Wherein, M¹¹Representation metal ion; L¹¹, L¹², L¹³, L¹⁴And L¹⁵Represent separately and M¹¹The part of coordination; L¹¹And L¹⁴Be not joined together to form the ring-type part by atomic group; L¹⁵Not with L¹¹And L¹⁴Bonding is to form the ring-type part; Y¹¹, Y¹²And Y¹³Represent linking group, singly-bound or two key separately; L¹¹And Y¹²Between key, Y¹²And L¹²Between key, L¹²And Y¹¹Between key, Y¹¹And L¹³Between key, L¹³And Y¹³Between key and Y¹³And L¹⁴Between key represent singly-bound or two key separately; n¹¹Represent 0 to 4.

[6] as each described Organnic electroluminescent device of [1]-[5], wherein said metal complex is the compound by formula (2) representative:

Formula (2)

Wherein, M²¹Representation metal ion; Y²¹Represent linking group, singly-bound or two key; Y²²And Y²³Represent singly-bound or linking group separately; Q²¹And Q²²Representative forms the atomic group of nitrogen heterocyclic ring necessity separately; Y²¹With by Q²¹Key and Y between the ring that forms²¹With by Q²²Key between the ring that forms is represented singly-bound or two key separately; X²¹And X²²Represention oxygen atom, sulphur atom or replacement or unsubstituted nitrogen-atoms separately; R²¹, R²², R²³And R²⁴Represent hydrogen atom or substituting group separately, R²¹And R²², and R²³And R²⁴Can be separately each other bonding to form ring; L²⁵Representative and M²¹The part of coordination; n²¹Represent 0 to 4 integer.

[7] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each pyridine ring naturally of the ring that forms, and Y²¹The linking group that representative is made up of at least one atom.

[8] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each pyridine ring naturally of the ring that forms, and Y²¹Represent singly-bound or two key, and X²¹And X²²Represent sulphur atom or replacement or unsubstituted nitrogen-atoms separately.

[9] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each 5 member heterocyclic ring containing nitrogen naturally of the ring that forms.

[10] as [6] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each contains 6 yuan of heterocycles of at least two nitrogen-atoms naturally the ring that forms.

[11] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (9) representative:

Formula (9)

Wherein, M^A1Representation metal ion; Q^A1And Q^A2Representative forms the atomic group of nitrogen heterocyclic ring necessity separately; R^A1, R^A2, R^A3And R^A4Represent hydrogen atom or substituting group separately; R^A1And R^A2, and R^A3And R^A4Can be respectively each other bonding to form ring; Y^A2And Y^A3Represent linking group or singly-bound separately; Y^A1Represent linking group, singly-bound or two key so that two two parts in bracket are linked together; L^A5Representative and M^A1The part of coordination; n^A1Represent 0 to 4 integer.

[12] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (10) representative,

Formula (10)

Wherein, M^B1Representation metal ion; Y^B1Represent linking group; Y^B2And Y^B3Represent linking group or singly-bound separately; X^B1And X^B2Represention oxygen atom, sulphur atom or replacement or unsubstituted nitrogen-atoms separately; n^B1And n^B2Represent 0 to 1 integer separately; R^B1, R^B2, R^B3, R^B4, R^B5And R^B6Represent hydrogen atom or substituting group separately; R^B1And R^B2, and R^B3And R^B4Can be respectively each other bonding to form ring; L^B5Representative and M^B1The part of coordination; n^B3Represent 0 to 4 integer; Y^B1Not with R^B5Or R^B6Connect.

[13] as each described Organnic electroluminescent device of [1]-[4], wherein said metal complex is the compound by formula (8) representative,

Formula (8)

Wherein, M⁸¹Representation metal ion; L⁸¹, L⁸², L⁸³And L⁸⁵Represent separately and M⁸¹The part of coordination; L⁸¹And L⁸³Be not joined together to form ring-type part or tetradentate ligands or higher multidentate ligand by atomic group; L⁸⁵Not directly and L⁸¹Or L⁸³Bonding, but pass through metal bonding; Y⁸¹And Y⁸²Represent linking group, singly-bound or two key separately; n⁸¹Represent 0 to 3 integer.

[14] as [13] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (8) representative, wherein L⁸¹, L⁸²And L⁸³Represent separately by carbon atom and M⁸¹The aromatic carbocyclic of coordination or heterocycle, or by nitrogen-atoms and M⁸¹The nitrogen heterocyclic ring of coordination; And L⁸¹, L⁸²And L⁸³In be described nitrogen heterocyclic ring one of at least.

[15] as [1] or [2] described Organnic electroluminescent device, wherein said metal complex is the compound by formula (X1) representative:

Formula (X1)

Wherein, M^X1Representation metal ion; QX¹¹, QX¹², QX¹³, QX¹⁴, QX¹⁵And QX¹⁶Represent separately and M^X1The atom of coordination or have and M^X1The atomic group of the atom of coordination; L^X11, L^X12, L^X13And L^X14Represent singly-bound, two key or linking group separately; By Q^X11-L^X11-Q^X12-L^X12-Q^X13The atomic group of forming and by Q^X14-L^X13-Q^X15-L^X14-Q^X16The atomic group of forming is represented tridentate ligand separately; M^X1And Q^X11Between key, M^X1And Q^X12Between key, M^X1And Q^X13Between key, M^X1And Q^X14Between key, M^X1And Q^X15Between key and M^X1And Q^X16Between key each coordinate bond or covalent bond naturally.

[16] as [15] described Organnic electroluminescent device, wherein said metal complex by formula (X1) representative is the compound by formula (X2) representative:

Formula (X2)

Wherein, M^X2Representation metal ion; Y^X21, Y^X22, Y^X23, Y^X24, Y^X25And Y^X26Represent separately and M^X2The atom of coordination; Each Q^X21, Q^X22, Q^X23, Q^X24, Q^X25And Q^X26Representative and each Y^X21, Y^X22, Y^X23, Y^X24, Y^X25And Y^X26Form the atomic group of aromatic ring or heterocycle necessity; L^X21, L^X22, L^X23And L^X24Represent singly-bound, two key or linking group separately; M^X2And Y^X21Between key, M^X2And Y^X22Between key, M^X2And Y^X23Between key, M^X2And Y^X24Between key, M^X2And Y^X25Between key and M^X2And Y^X26Between key each coordinate bond or covalent bond naturally.

[17] as [15] described Organnic electroluminescent device, wherein said metal complex by formula (X1) representative is the compound by formula (X3) representative:

Formula (X3)

Wherein, M^X3Representation metal ion; Y^X31, Y^X32, Y^X33, Y^X34, Y^X35And Y^X36Represent carbon atom, nitrogen-atoms or phosphorus atoms separately; L^X31, L^X32, L^X33And L^X34Represent singly-bound, two key or linking group separately; M^X3And Y^X31Between key, M^X3And Y^X32Between key, M^X3And Y^X33Between key, M^X3And Y^X34Between key, M^X3And Y^X35Between key and M^X3And Y^X36Between key each coordinate bond or covalent bond naturally.

[18] as each described Organnic electroluminescent device of [1]-[17], wherein said organic layer comprises at least one luminescent layer and hole transmission layer, and described organic layer also comprises the layer that at least one is selected from exciton barrier-layer, hole injection layer, hole blocking layer and electron transfer layer.

[19] as each described Organnic electroluminescent device of [1]-[18], wherein said organic layer comprises at least one luminescent layer, and the material of main part of described luminescent layer is selected from amines, the accurate oxide of metal-chelating (compound that promptly has metal-oxygen key), and wherein said metal is aluminium, zinc or transition metal, polyarylene compound, fused aromatic carbocyclic compound and non-complexing aromatic heterocycle compounds.

[20] as each described Organnic electroluminescent device of [1]-[19], wherein said organic layer comprises at least one electron transfer layer, and wherein electron transport material is selected from the accurate oxide of metal-chelating, polyarylene compound, fused aromatic carbocyclic compound and non-complexing aromatic heterocycle compounds.

[21] as each described Organnic electroluminescent device of [1]-[20], wherein said organic layer comprises at least one luminescent layer, and the material of main part of described luminescent layer is made up of at least two kinds of compounds.

[22] compound of representing by formula (11):

Formula (11)

Wherein, R^C1And R^C2Represent hydrogen atom or substituting group separately; R^C3, R^C4, R^C5And R^C6Represent substituting group separately; n^C3And n^C6Represent 0 to 3 integer separately; n^C4And n^C5Represent 0 to 4 integer separately; When there being a plurality of R^C3, R^C4, R^C5Or R^C6The time, each R^C3, R^C4, R^C5Or R^C6Can be same to each other or different to each other, and a plurality of R^C3, R^C4, R^C5Or R^C6Separately each other bonding to form condensed ring.

[23] compound of representing by formula (12):

Formula (12)

Wherein, R^D3And R^D4Represent hydrogen atom or substituting group separately; R^D1And R^D2Represent substituting group separately; n^D1And n^D2Represent 0 to 4 integer separately; When there being a plurality of R^D1Or R^D2The time, each R^D1Or R^D2Can be same to each other or different to each other, and a plurality of R^D1Or R^D2Bonding is to form ring each other; Y^D1Representative has vinyl, phenylene, pyridine ring, pyrazine ring, the pyrimidine ring of replacement in 1-and 2-position or has the alkylidene of 1 to 8 carbon atom.

[24] compound of representing by formula (X1):

Formula (X1)

Wherein, M^X1Representation metal ion; Q^X11, Q^X12, Q^X13, Q^X14, Q^X15And Q^X16Represent separately and M^X1The atom of coordination or have and M^X1The atomic group of the atom of coordination; L^X11, L^X12, L^X13And L^X14Represent singly-bound, two key or linking group separately; By Q^X11-L^X11-Q^X12-L^X12-Q^X13The atomic group of forming and by Q^X14-L^X13-Q^X15-L^X14-Q^X16The atomic group of forming is represented tridentate ligand separately; M^X1And Q^X11Between key, M^X1And Q^X12Between key, M^X1And Q^X13Between key, M^X1And Q^X14Between key, M^X1And Q^X15Between key and M^X1And Q^X16Between key each coordinate bond or covalent bond naturally.

[25] compound of representing by formula (X2):

Formula (X2)

Wherein, M^X2Representation metal ion; Y^X21, Y^X22, Y^X23, Y^X24, Y^X25And Y^X26Represent separately and M^X2The atom of coordination; Each Q^X21, Q^X22, Q^X23, Q^X24, Q^X25And Q^X26Representative and each Y^X21, Y^X22, Y^X23, Y^X24, Y^X25And Y^X26The atomic group of each self-forming aromatic ring or heterocycle necessity; L^X21, L^X22, L^X23And L^X24Represent singly-bound, two key or linking group separately; M^X2And Y^X21Between key, M^X2And Y^X22Between key, M^X2And Y^X23Between key, M^X2And Y^X24Between key, M^X2And Y^X25Between key and M^X2And Y^X26Between key each coordinate bond or covalent bond naturally.

[26] compound of representing by formula (X3):

Formula (X3)

Used in this manual term " chain part " is meant and removes for example part of porphyrin and phthalocyanine of decyclization part.With formula (8) is example, and described term is not meant and directly links to each other, but passes through Y⁸¹, L⁸², Y⁸²And M⁸¹And the ligand L that links to each other⁸¹And L⁸³Even working as L⁸¹, Y⁸¹, L⁸², Y⁸²Or L⁸³Contain in the situation of ring structure such as benzene, pyridine and quinoline, described part is meant the chain part, as long as L⁸¹And L⁸³Directly do not link to each other, but pass through Y⁸¹, L⁸², Y⁸²And M⁸¹And link to each other.Can be at L⁸¹And Y⁸¹, or Y⁸¹And L⁸², or L⁸²And Y⁸², or Y⁸²And L⁸³Between exist other aromatic group to form ring.

Below will be more comprehensively and describe other and other characteristic and advantage of the present invention in detail.

Embodiment

Organnic electroluminescent device of the present invention (this and after be sometimes referred to as device of the present invention) be characterised in that and it comprise pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes (described organic layer can include organic compounds, or comprise inorganic compound in addition), wherein the arbitrary layer between described pair of electrodes comprises the phosphorescent metal complex with three toothed chain parts or higher multiple tooth chain part.

As the metal complex that uses among the present invention with three toothed chain parts or higher multiple tooth chain part (this and after be sometimes referred to as metal complex of the present invention), preferably has metal complex from three teeth to octadentate chain part, more preferably has metal complex from four teeth to octadentate chain part, be more preferably the metal complex that has from four tooth to six toothed chain parts, most preferably have the metal complex of four toothed chain parts.

The chain part that uses among the present invention preferably contains at least one nitrogen heterocyclic ring (for example pyridine, quinoline, pyrrole ring) so that (as if being example with formula (1), then described metal is M with major metal through nitrogen-atoms¹¹) coordination.

Preferred metal complex of the present invention is carbon containing-metallic bond not.Also be between metallic atom and carbon atom, not become key in the preferable alloy complex compound.Especially about term " not carbon containing-metallic bond ", the preferable alloy complex compound has following arbitrary key.Also be preferred containing metal-nitrogen key, metal-oxygen key, metal-sulfur key, metal-phosphorus key and metal-selenium key.More preferably metal-nitrogen key, metal-oxygen key, metal-sulfur key and metal-phosphorus key.Be more preferably metal-nitrogen key, metal-oxygen key and metal-sulfur key.

Compound used among the present invention is not particularly limited, as long as this compound is phosphorescent compound.Preferably be not less than-30 ℃ of phosphorescent compounds, more preferably be not less than-10 ℃, be more preferably at and be not less than 0 ℃, and particularly preferably in being not less than 10 ℃.This compound can fluoresce simultaneously.In this case, preferably this compound is not less than 2 times of its fluorescence intensity at 20 ℃ phosphorescence intensity, more preferably is not less than 10 times, is more preferably and is not less than 100 times.

Used phosphor material has and is not less than 10% phosphorescence quantum yield (20 ℃) and phosphorescence λ among preferred the present invention_Max(emission maximum phosphorescence) in the scope of 400nm to 700nm, more preferably phosphorescence quantum yield (20 ℃) is not less than 15% and phosphorescence λ_MaxIn the scope of 400nm to 575nm, be more preferably phosphorescence quantum yield (20 ℃) and be not less than 20% and phosphorescence λ_MaxIn the scope of 400nm to 560nm.

Metal complex of the present invention is incorporated in the arbitrary layer between the pair of electrodes, preferably it is incorporated in hole injection/hole transmission layer and/or luminescent layer, more preferably it is incorporated in luminescent layer.Metal complex of the present invention is being incorporated in the situation of luminescent layer, the phosphorescent compound concentrations in the luminescent layer is 1-30 weight % based on the weight of luminescent layer separately, and more preferably 2-20 weight % is more preferably 3-15 weight %.

A preferred implementation of metal complex of the present invention has by the quadridentate ligand of formula (1) representative or higher multidentate ligand.Preferred implementation by the metal complex of formula (1) representative is by formula (2), (5), (9) or (10) representative.

Formula (5)

By the preferred implementation of the metal complex of formula (2) representative by formula (3) representative.

Formula (3)

By the preferred implementation of the metal complex of formula (9) representative by formula (6) or formula (7) representative, and by the preferred implementation of the metal complex of formula (7) representative by formula (11) representative.

By the preferred implementation of the metal complex of formula (10) representative by formula (12) representative.

Formula (6)

Formula (7)

Compound by formula (1) representative below will be described.

M¹¹Representation metal ion.This metal ion is not particularly limited, but preferably divalence or trivalent metal ion.As divalence or trivalent metal ion, preferred platinum, iridium, rhenium, palladium, rhodium, ruthenium, copper, europium, gadolinium and terbium ion.More preferably platinum, iridium and europium ion in these ions are more preferably platinum and iridium ion, especially preferred platinum ion.

L¹¹, L¹², L¹³And L¹⁴Represent separately and M¹¹The part of coordination.As being contained in L¹¹, L¹², L¹³Or L¹⁴In and and M¹¹The atom of coordination, preferred nitrogen, oxygen, sulphur and carbon atom are more preferably nitrogen, oxygen and carbon atom.

At M¹¹And L¹¹, L¹², L¹³Or L¹⁴Between the key that forms can be covalent bond, ionic bond or coordinate bond.Comprise L¹¹, Y¹², L¹², Y¹¹, L¹³, Y¹³And L¹⁴Part anion ligand (being at least one anion and the metal bonding of part) preferably.Anion number in the anion ligand is 1-3 preferably, is more preferably 1 or 2, and being more preferably is 2.

L¹¹, L¹², L¹³Or L¹⁴Through carbon atom and M¹¹Coordination is not particularly limited this.The example of these parts comprises imino group part, aromatic carbocyclic part (for example benzene, naphthalene, anthracene, benzene anthracene part), heterocyclic ligand (for example thiophene, pyridine, pyrazine, pyrimidine, thiazole, azoles, pyrroles, imidazoles, pyrazoles part, the condensed ring (for example quinoline, benzothiazole part) that contains these rings and the dynamic isomer of these rings).

L¹¹, L¹², L¹³Or L¹⁴Through nitrogen-atoms and M¹¹Coordination is not particularly limited this.The example of these parts comprises that (for example (Ding Yi dynamic isomer also can comprise the dynamic isomer of following example and common dynamic isomer to the nitrogen heterocyclic ring part in the present invention for pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, imidazoles, pyrazoles, triazole, oxadiazole and thiadiazoles part, the condensed ring (for example quinoline, benzoxazole, benzimidazole part) that comprises any these parts and the dynamic isomer of these parts; 5 yuan of heterocyclic ligands of compound (24) for example; 5 yuan of heterocyclic ligands of the end of compound (64); and 5 yuan of heterocyclic ligands of compound (145) are defined as pyrroles's dynamic isomer)); and amino ligands (for example the alkyl amino part (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-10 carbon atom; methylamino for example); virtue amino ligands (for example phenylamino); amido ligands (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; those of preferred especially 2-10 carbon atom; acetylamino for example; benzamido); the alkoxycarbonyl ammonia ylidene ligands (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-12 carbon atom; methoxycarbonyl amino for example); the aryloxycarbonyl amino ligands (preferably has 7-30 carbon atom; more preferably have 7-20 carbon atom; especially preferably have those of 7-12 carbon atom; phenyloxycarbonyl amino for example); the Herbicidal sulphonylamino ylidene ligands (preferably has 1-30 carbon atom; more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, for example sulfonyl methane amino; benzenesulfonamido-), imino group part).These parts can also be substituted base and replace.

L¹¹, L¹², L¹³Or L¹⁴Through oxygen atom and M¹¹Coordination is not particularly limited this.The example of these parts comprises that alkoxy ligand (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-10 carbon atom, methoxyl group for example, ethyoxyl, butoxy, the 2-ethyl hexyl oxy), aryloxy ligands (preferably has 6-30 carbon atom, more preferably have 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, phenoxy group for example, the 1-naphthoxy, the 2-naphthoxy), the heterocyclic oxy group part (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridine oxygen base for example, pyrazoles oxygen base, 2-pyrimidinyl oxy, quinoline oxy), acyloxy (preferably has 2-30 carbon atom, more preferably have 2-20 carbon atom, especially preferably have those of 2-10 carbon atom, for example acetoxyl group, benzoyloxy), silyloxy (preferably has 3-40 carbon atom, more preferably has 3-30 carbon atom, especially preferably have those of 3-24 carbon atom, trimethyl silyloxy for example, the triphenyl silyloxy), carbonyl ligands (ketone part for example, ester part, amide ligands), with ether part (for example dialkyl ether part, diaryl ether part, furyl part).

L¹¹, L¹², L¹³Or L¹⁴Through sulphur atom and M¹¹Coordination is not particularly limited this.The example of these parts comprises that the alkylthio part (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, methyl sulphur for example, ethyl sulphur), aryl sulfo-part (preferably has 6-30 carbon atom, more preferably has 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, phenyl sulphur for example), heterocycle sulfo-part (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridine sulphur for example, 2-benzimidazole sulphur, 2-benzoxazole sulphur, 2-[4-morpholinodithio sulphur), thiocarbonyl part (for example thioketones part, thioester part) and thioether part (dialkyl sulfide part for example, the diaryl sulfide part, sulphur furans part).And these parts can also be substituted base and replace.

Preferably, L¹¹And L¹⁴Each is the aromatic carbocyclic part naturally, alkoxy ligand, aryloxy ligands, ether part, alkylthio part, aryl sulfo-part, alkyl amino part, fragrant amino ligands, amido ligands, with nitrogen heterocyclic ring part (pyridine for example, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, imidazoles, pyrazoles, triazole ， oxadiazole, with the thiadiazoles part, contain arbitrarily the condensation part of these parts (for example quinoline, benzoxazole, benzimidazole part); Dynamic isomer with any these parts).In these parts, more preferably aromatic carbocyclic part, aryloxy ligands, aryl sulfo-part, fragrant amino ligands, pyridine ligand, the pyrazine part, imidazole ligands contains arbitrarily the condensation part of these parts (for example quinoline, quinoxaline, benzimidazole part); Dynamic isomer with any these parts.Be more preferably the aromatic carbocyclic part, aryloxy ligands, aryl sulfo-part and fragrant amino ligands, most preferably aromatic carbocyclic part and aryloxy ligands.

L¹²And L¹³Separately preferably with M¹¹Form the part of coordinate bond.As forming the part of coordinate bond with M11, preferred pyridine ring, the pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, the azoles ring, pyrrole ring, triazole ring contains the condensed ring (for example, quinoline, benzoxazole, benzimidazole and indolenine ring) of these rings arbitrarily; Dynamic isomer with any these rings.Wherein preferred pyridine ring, the pyrazine ring, pyrimidine ring, pyrrole ring contains arbitrarily the condensed ring of these rings (for example quinoline, indole ring); Dynamic isomer with any these rings.Be more preferably pyridine ring, the pyrazine ring, pyrimidine ring contains the condensed ring (for example quinoline ring) of these rings arbitrarily.Preferred especially pyridine ring and the condensed ring (for example quinoline ring) that contains pyridine ring.

L¹⁵Representative and M¹¹The part of coordination.L¹⁵Preferably monodentate is more preferably anionic monodentate to quadridentate ligand to quadridentate ligand.This anionic monodentate to quadridentate ligand is had no particular limits, but halogen ligands preferably, 1,3-diketonate ligand (for example acetyl acetone ligands), the single anion bidentate ligand (for example pyridine carboxylic acid, 2-(2-hydroxy phenyl)-pyridine ligand) and and the L that contain pyridine ligand¹¹, Y¹², L¹², Y¹¹, L¹³, Y¹³And L¹⁴The quadridentate ligand that forms; More preferably 1,3-diketonate ligand (for example acetyl acetone ligands) contains the single anion bidentate ligand (for example pyridine carboxylic acid, 2-(2-hydroxy phenyl)-pyridine ligand) and and the L of pyridine ligand¹¹, Y¹², L¹², Y¹¹, L¹³, Y¹³And L¹⁴The quadridentate ligand that forms; Be more preferably 1,3-diketonate ligand (for example acetyl acetone ligands) contains the single anion bidentate ligand (for example pyridine carboxylic acid, 2-(2-hydroxy phenyl)-pyridine ligand) of pyridine ligand; Especially preferred 1,3-diketonate ligand (for example acetyl acetone ligands).Ligancy and part number are no more than the ligancy of metal.L¹⁵All not with L¹¹And L¹⁴Be joined together to form the ring-type part.

Y¹¹, Y¹²And Y¹³Represent linking group separately, singly-bound or two key.Linking group is not particularly limited.The example of linking group comprises carbonyl linking, thiocarbonyl linking group, alkylidene, alkenylene, arlydene, heteroarylidene, oxygen atom linking group, nitrogen-atoms linking group, silicon atom linking group and contain the linking group of the combination of these groups.L¹¹And Y¹²Between key, Y¹²And L¹²Between key, L¹²And Y¹¹Between key, Y¹¹And L¹³Between key, L¹³And Y¹³Between key, and Y¹³And L¹⁴Between key represent singly-bound separately, or two key.

Y¹¹, Y¹²And Y¹³Singly-bound preferably separately, two keys, carbonyl linking, alkylidene linking group or alkenylene.Y¹¹Be more preferably singly-bound or alkylidene, being more preferably is alkylidene.Y¹²And Y¹³Preferably singly-bound or alkenylene separately, being more preferably is singly-bound.

By Y¹², L¹¹, L¹²And M¹¹The ring that forms is by Y¹¹, L¹², L¹³And M¹¹The ring that forms, and by Y¹³, L¹³, L¹⁴And M¹¹The number of members of the ring that forms is preferably 4-10 separately, is more preferably 5-7, is preferably 5 or 6 especially.

n¹¹Represent 0 to 4.Work as M¹¹Be when to have ligancy be 4 metal, n¹¹Be 0.Work as M¹¹Be when to have ligancy be 6 metal, n¹¹Preferably 1 or 2, being more preferably is 1.Work as M¹¹Be that to have ligancy be 6 metal and n¹¹Be 1 o'clock, L¹⁵Represent bidentate ligand.Work as M¹¹Be that to have ligancy be 6 metal and n¹¹Be 2 o'clock, L¹⁵Represent monodentate ligand.Work as M¹¹Be when to have ligancy be 8 metal, n¹¹1-4 preferably, being more preferably is 1 or 2, especially preferably 1.Work as M¹¹Be that to have ligancy be 8 metal and n¹¹Be 1 o'clock, L¹⁵Represent quadridentate ligand, and work as n¹¹Be 2 o'clock, L¹⁵Represent bidentate ligand.Work as n¹¹Be 2 or when bigger, a plurality of L¹⁵Can be same to each other or different to each other.

Next, the compound of being represented by formula (2) will be described.

M²¹Have and aforementioned M¹¹Identical implication and identical preferable range.

Q²¹And Q²²Representative formation nitrogen heterocyclic ring (contains and M separately²¹The ring of the nitrogen-atoms of coordination) group.To by Q²¹Or Q²²The nitrogen heterocyclic ring that forms has no particular limits, and the example comprises pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, the azoles ring, pyrrole ring, triazole ring contains arbitrarily the condensed ring of these rings (for example quinoline benzoxazole, benzimidazole and indolenine ring), and the dynamic isomer of these rings.

By Q²¹Or Q²²The nitrogen heterocyclic ring that forms is pyridine ring preferably, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, the pyrazoles ring, imidazole ring, azoles ring, pyrrole ring, indole ring, contain arbitrarily the condensed ring of these rings (for example quinoline, benzoxazole and benzimidazole ring), and the dynamic isomer of these rings arbitrarily.By Q²¹Or Q²²It is pyridine ring that the nitrogen heterocyclic ring that forms is more preferably, the pyrazine ring, and pyrimidine ring, imidazole ring, pyrrole ring contains the condensed ring (for example quinoline ring) of these rings arbitrarily, and the dynamic isomer of these rings arbitrarily.By Q²¹Or Q²²The nitrogen heterocyclic ring that forms is pyridine ring especially preferably, contains the condensed ring (for example quinoline ring) of pyridine ring, especially preferably pyridine ring.

X²¹And X²²Oxygen atom preferably separately, sulphur atom, or replacement or unsubstituted nitrogen-atoms.They are more preferably separately is oxygen atom, sulphur atom, or the nitrogen-atoms that replaces, further preferably oxygen atom or sulphur atom, especially preferably oxygen atom.

Y²¹Have and aforementioned Y¹¹Identical implication and identical preferable range.

Y²²And Y²³Represent singly-bound or linking group separately, preferably singly-bound.Linking group is had no particular limits.The example of linking group comprises carbonyl linking, thiocarbonyl linking group, alkylidene, alkenylene, arlydene, heteroarylidene, oxygen atom linking group, nitrogen-atoms linking group and contain the linking group that these groups make up arbitrarily.

As above-mentioned linking group, preferred carbonyl linking, alkylidene linking group, alkenylene linking group.Wherein more preferably carbonyl linking and alkenylene linking group are more preferably carbonyl linking.

R²¹, R²², R²³And R²⁴Represent hydrogen atom or substituting group separately.Substituting group is had no particular limits.Substituent example comprises that alkyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-10 carbon atom; methyl for example, ethyl, isopropyl; the tert-butyl group, n-octyl, positive decyl; n-hexadecyl, cyclopropyl, cyclopenta; cyclohexyl), alkenyl (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom; especially preferably have 2-10 carbon atom, vinyl for example, pi-allyl; the 2-cyclobutenyl, the 3-pentenyl), alkynyl (preferably has 2-30 carbon atom; be more preferably and have 2-20 carbon atom, especially preferably have 2-10 carbon atom, for example propargyl; the 3-pentynyl), aryl (preferably has 6-30 carbon atom, is more preferably and has 6-20 carbon atom; especially preferably have 6-12 carbon atom, phenyl for example, p-methylphenyl; naphthyl, anthryl), amino (preferably have 0-30 carbon atom; be more preferably and have 0-20 carbon atom, especially preferably have 0-10 carbon atom, for example amino; methylamino, dimethylamino, diethylamino; dibenzyl amino, diphenyl amino, dimethylbenzene amino); alkoxyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-10 carbon atom; methoxyl group for example, ethyoxyl, butoxy; the 2-ethyl hexyl oxy), aryloxy group (preferably has 6-30 carbon atom, is more preferably and has 6-20 carbon atom; especially preferably have 6-12 carbon atom, phenoxy group for example, 1-naphthoxy; the 2-naphthoxy), heterocyclic oxy group (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, pyridine oxygen base for example, pyrazine oxygen base; 2-pyrimidinyl oxy, quinoline oxy), acyl group (preferably has 1-30 carbon atom; be more preferably and have 1-20 carbon atom, especially preferably have 1-12 carbon atom, for example acetyl group; benzoyl, formoxyl, valeryl); alkoxy carbonyl group (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom, especially preferably have 2-12 carbon atom; methoxycarbonyl group for example, carbethoxyl group), aryloxy carbonyl (preferably has 7-30 carbon atom; be more preferably and have 7-20 carbon atom, especially preferably have 7-12 carbon atom, for example carbobenzoxy); acyloxy (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom, especially preferably have 2-10 carbon atom; acetoxyl group for example, benzoyloxy), acylamino-(preferably has 2-30 carbon atom; be more preferably and have 2-20 carbon atom, especially preferably have 2-10 carbon atom, for example acetylamino; benzamido), alkoxycarbonyl amido (preferably has 2-30 carbon atom, is more preferably and has 2-20 carbon atom; especially preferably have 2-12 carbon atom, for example methoxycarbonyl group amino), aryloxy carbonyl amino (preferably has 7-30 carbon atom; be more preferably and have 7-20 carbon atom, especially preferably have 7-12 carbon atom, for example phenyloxycarbonyl amino); sulfonamido (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; sulfonyl methane amino for example, benzenesulfonamido-), sulfamoyl (preferably has 0-30 carbon atom; be more preferably and have 0-20 carbon atom, especially preferably have 0-12 carbon atom, for example sulfamoyl; the methyl sulfamoyl, dimethylamino sulfonyl, phenyl sulfamoyl base); carbamoyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; carbamoyl for example, methylamino formoxyl, diethylamino formoxyl; the phenyl amino formoxyl), alkyl thio-base (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, methyl sulfenyl for example, ethyl sulfenyl); the aryl thio group (preferably has 6-30 carbon atom, is more preferably and has 6-20 carbon atom, especially preferably have 6-12 carbon atom; phenyl sulfenyl for example), the heterocycle thio group (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, pyridine sulfenyl for example, 2-benzimidazole sulfenyl; 2-benzoxazole sulfenyl, the 2-[4-morpholinodithio sulfenyl), sulfonyl (preferably has 1-30 carbon atom; be more preferably and have 1-20 carbon atom, especially preferably have 1-12 carbon atom, for example mesyl; tosyl), sulfinyl (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom; especially preferably have 1-12 carbon atom, methanesulfinyl for example, phenylsulfinyl base); urea groups (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; urea groups for example, methyl urea groups, phenyl urea groups); the phosphoamide base (preferably has 1-30 carbon atom, is more preferably and has 1-20 carbon atom, especially preferably have 1-12 carbon atom; diethyl phosphinylidyne amido for example, phenyl phosphinylidyne amido), hydroxyl; sulfydryl, halogen atom (fluorine for example, chlorine; bromine; iodine), cyano group, sulfo group; carboxyl; nitro, hydroxamic acid base, sulfino; diazanyl; imino group, heterocyclic radical (preferably has 1-30 carbon atom, is more preferably and has 1-12 carbon atom; and contain hetero-atom such as nitrogen; oxygen and sulphur, instantiation are imidazole radicals, pyridine radicals; quinolyl; furyl, thienyl, piperidyl; morpholino base benzoxazolyl, benzimidazolyl, benzothiazolyl; carbazyl; the azepine base), silicyl (preferably has 3-40 carbon atom, is more preferably and has 3-30 carbon atom; especially preferably have 3-24 carbon atom; trimethyl silyl for example, the triphenyl silicyl), silyloxy (preferably has 3-40 carbon atom; be more preferably and have 3-30 carbon atom; especially preferably have 3-24 carbon atom, trimethyl silyloxy for example, triphenyl silyloxy).These substituting groups can also be substituted.

Preferably, R²¹, R²², R²³And R²⁴Each alkyl naturally, aryl is by at R²¹And R²², or R²³And R²⁴Between become key to form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Be more preferably R²¹, R²², R²³And R²⁴Each passes through naturally at R²¹And R²², or R²³And R²⁴Between become key to form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).

L²⁵Have and aforementioned L¹⁵Identical implication and identical preferable range.

n²¹Have and aforementioned n¹¹Identical implication and identical preferable range.

In the metal complex by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each pyridine ring naturally of the ring that forms, and Y²¹Represent linking group; Wherein by Q²¹The ring that forms and by Q²²Each pyridine ring naturally of the ring that forms, and Y²¹Represent singly-bound or two key, and X²¹And X²²Represent sulphur atom or replacement or unsubstituted nitrogen-atoms separately; Wherein by Q²¹The ring that forms and by Q²²Each nitrogenous naturally 5 yuan of heterocycle of the ring that forms or the nitrogenous 6 yuan of heterocycles that contain two or more nitrogen-atoms all are preferred.

Next, the compound of being represented by formula (3) is described.

M³¹Have and aforementioned M¹¹Identical implication and identical preferable range.

Z³¹, Z³², Z³³, Z³⁴, Z³⁵And Z³⁶Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example on carbon atom is included in aforementioned R²¹Middle those that explain.In addition, Z³¹And Z³², Z³²And Z³³, Z³³And Z³⁴, Z³⁴And Z³⁵, Z³⁵And Z³⁶Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).Perhaps Z³¹And T³¹, Z³⁶And T³⁸Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).

As aforementioned substituting group on carbon atom, preferred alkyl, alkoxyl, alkyl amino, aryl forms the group and the halogen atom of condensed ring (for example fused benzo ring, pyridine condensed ring).Wherein, be more preferably alkyl amino, aryl and form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Further preferred aryl groups and form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Most preferably form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).

T³¹, T³², T³³, T³⁴, T³⁴, T³⁶, T³⁷And T³⁸Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example is included in aforementioned R on carbon atom²¹Middle those that explain.T³¹And T³², T³²And T³³, T³³And T³⁴, T³⁵And T³⁶, T³⁶And T³⁷, T³⁷And T³⁸Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring).

As aforementioned substituting group on carbon atom, preferred alkyl, alkoxyl, alkyl amino, aryl forms the group and the halogen atom of condensed ring (for example fused benzo ring, pyridine condensed ring).Wherein, be more preferably aryl, form the group of condensed ring (for example fused benzo ring, pyridine condensed ring), and halogen atom.Further preferred aryl groups and halogen atom.Aryl most preferably.

X³¹And X³²Have and aforementioned X²¹And X²²Identical implication and identical preferable range.

Next, the compound of being represented by formula (5) is described.

M⁵¹Have and aforementioned M¹¹Identical implication and identical preferable range.

Q⁵¹And Q⁵²Have and aforementioned Q²¹And Q²²Identical implication and identical preferable range.

Q⁵³And Q⁵⁴Representative formation nitrogen heterocyclic ring (contains and M separately⁵¹The ring of the nitrogen-atoms of coordination) group.To by Q⁵³Or Q⁵⁴The nitrogen heterocyclic ring that forms has no particular limits, but the dynamic isomer of azole derivatives preferably, the dynamic isomer of imdazole derivatives (for example 5 yuan of heterocyclic ligands of compound (29)), the dynamic isomer (for example 5 yuan of heterocyclic ligands of compound (31)) of dynamic isomer of thiazole (for example 5 yuan of heterocyclic ligands of compound (30)) and Zole derivatives, be more preferably the dynamic isomer of azole derivatives, the dynamic isomer of imdazole derivatives, dynamic isomer with thiazole, the dynamic isomer of further preferred azole derivatives and the dynamic isomer of imdazole derivatives, the dynamic isomer of preferred especially azole derivatives.

Y⁵¹Have and aforementioned Y¹¹Identical implication and identical preferable range.

L⁵⁵Have and aforementioned L¹⁵Identical implication and identical preferable range.

n⁵¹Have and aforementioned n¹¹Identical implication and identical preferable range.

W⁵¹And W⁵²Preferably replace separately or unsubstituted carbon atom or nitrogen-atoms.They are more preferably separately is unsubstituted carbon atom or nitrogen-atoms, further preferably unsubstituted carbon atom.

The compound of next, description formula (9) representative.

M^A1, Q^A1, Q^A2, Y^A1, Y^A2, Y^A3, R^A1, R^A2, R^A3, R^A4, L^A5And n^A1Have respectively separately and the middle M of aforementioned formula (2)²¹, Q²¹, Q²², Y²¹, Y²², Y²³, R²¹, R²², R²³, R²⁴, L²⁵And n²¹Identical implication and identical preferable range.

The compound of next, description formula (6) representative.

M⁶¹Have and aforementioned M¹¹Identical implication and identical preferable range.

Q⁶¹And Q⁶²Representative forms the group of ring separately.To by Q⁶¹Or Q⁶²The ring that forms has no particular limits.As described ring, for example benzene, pyridine, pyridazine, pyrimidine, thiophene, isothiazole, furans ， isoxazole ring and their condensed ring.

By Q⁶¹Or Q⁶²The ring that forms is benzene preferably, pyridine, and thiophene, or thiazole ring, or their condensed ring, being more preferably is benzene or pyridine ring, or their condensed ring, further preferably phenyl ring and its condensed ring.

Y⁶¹Have and aforementioned Y¹¹Identical implication and identical preferable range.

Y⁶²And Y⁶³Represent linking group or singly-bound separately.Linking group is had no particular limits.The example of linking group comprises carbonyl linking, thiocarbonyl linking group, alkylidene, alkenylene, arlydene, heteroarylidene, oxygen atom linking group, nitrogen-atoms linking group and by the linking group that is combined to form of these linking groups.

Preferred Y⁶²And Y⁶³Each singly-bound naturally, carbonyl linking, alkylidene linking group, or alkenylene, be more preferably them each singly-bound or alkenylene naturally, further singly-bound preferably.

L⁶⁵Have and aforementioned L¹⁵Identical implication and identical preferable range.

n⁶¹Have and aforementioned n¹¹Identical implication and identical preferable range.

z⁶¹, z⁶², z⁶³, z⁶⁴, z⁶⁵, z⁶⁶, z⁶⁷And z⁶⁸Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example comprises aforementioned R on the carbon atom²¹Middle those that explain.In addition, z⁶¹And z⁶², z⁶²And z⁶³, z⁶³And z⁶⁴, z⁶⁵And z⁶⁶, z⁶⁶And z⁶⁷, z⁶⁷And z⁶⁸Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).By Q⁶¹Or Q⁶²The ring that forms can be bonded to z by linking group separately⁶¹Or z⁶⁸To form ring.

As aforementioned substituting group on carbon atom, preferred alkyl, alkoxyl, alkyl amino, aryl forms the group and the halogen atom of condensed ring (for example fused benzo ring, pyridine condensed ring).Wherein, be more preferably arylamino, aryl forms the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Further preferred aryl groups and form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).Most preferably form the group of condensed ring (for example fused benzo ring, pyridine condensed ring).

The compound of next, description formula (7) representative.

M⁷¹Have and aforementioned M¹¹Identical implication and identical preferable range.

Y⁷¹, Y⁷²And Y⁷³Have separately and aforementioned Y⁶²Identical implication and identical preferable range.

L⁷⁵Have and aforementioned L¹⁵Identical implication and identical preferable range.

n⁷¹Have and aforementioned n¹¹Identical implication and identical preferable range.

z⁷¹, z⁷², z⁷³, z⁷⁴, z⁷⁵And z⁷⁶Representative replaces or unsubstituted carbon atom or nitrogen-atoms separately, wherein preferred the replacement or unsubstituted carbon atom.Substituent example comprises aforementioned at R on the carbon atom²¹Middle those that explain.In addition, z⁷¹And z⁷², and z⁷³And z⁷⁴Separately can by linking group each other bonding to form condensed ring (for example fused benzo ring, pyridine condensed ring).

R⁷¹, R⁷², R⁷³And R⁷⁴Separately with the middle R of aforementioned formula (2)²¹, R²², R²³And R²⁴Have identical implication and identical preferable range.

Next, the compound of being represented by formula (11) is described.

R^C1And R^C2Represent hydrogen atom or substituting group separately.Substituting group is suc as formula R in (2)²¹To R²⁴The cited alkyl or aryl of substituting group.R^C3, R^C4, R^C5And R^C6The substituting group of representative also with formula (2) in R²¹To R²⁴Cited have an identical implication.n^C3And n^C6Represent 0 to 3 integer separately; n^C4And n^C5Represent 0 to 4 integer separately.When there being two or more R^C3, R^C4, R^C5Or R^C6The time, they can be same to each other or different to each other, and they separately each other bonding to form ring.R^C3, R^C4, R^C5And R^C6Preferably alkyl, aryl, heteroaryl and halogen atom separately.

Next, the compound of being represented by formula (10) is described.

M^B1, Y^B2, Y^B3, R^B1, R^B2, R^B3, R^B4, L^B5, n^B3, X^B1And X^B2Have separately and the middle M of aforementioned formula (2)²¹, Y²², Y²³, R²¹, R²², R²³, R²⁴, L²⁵, n²¹, X²¹And X²²Identical implication and identical preferable range.Y^B1Representative and the middle Y of formula (2)²¹Identical linking group, the vinyl that on 1-and 2-position, replaces preferably, phenylene, pyridine ring, pyrazine ring, pyrimidine ring or have the alkylidene of 2 to 8 carbon atoms.R^B5And R^B6Represent hydrogen atom or substituting group separately.Described substituting group is R in the formula (2)²¹To R²⁴The alkyl that substituting group is cited, aryl or heterocyclic radical.Yet Y^B1Not with R^B5Or R^B6Connect.n^B1And n^B2Represent 0 to 1 integer separately.

Next, the compound of being represented by formula (12) is described.

R^D1, R^D2, R^D3And R^D4The substituting group of representative and the R in the formula (10)^B5And R^B6Have identical implication and identical preferable range.n^D1And n^D2Represent 0 to 4 integer separately.Y^D1Representative has vinyl, phenylene, pyridine ring, pyrazine ring, the pyrimidine ring of replacement in 1-and 2-position or has the alkylidene of 1 to 8 carbon atom.

According to the present invention, the preferred implementation that contains the metal complex of terdentate ligand is exemplified by formula (8).

Next, the compound of being represented by formula (8) is described.

M⁸¹Have and aforementioned M¹¹Identical implication and identical preferable range.

L⁸¹, L⁸²And L⁸³Have separately and aforementioned L¹¹, L¹²And L¹⁴Identical implication and identical preferable range.

Y⁸¹And Y⁸²Have separately and aforementioned Y¹¹And Y¹²Identical implication and identical preferable range.

L⁸⁵Representative and M⁸¹The part of coordination.L⁸⁵Preferably monodentate ligand is more preferably monodentate to three tooth anion ligand to terdentate ligand.Described monodentate to three tooth anion ligand is not particularly limited, but halogen ligands preferably, by L⁸¹, Y⁸¹, L⁸², Y⁸²And L⁸³The terdentate ligand that forms, being more preferably is by L⁸¹, Y⁸¹, L⁸², Y⁸²And L⁸³The terdentate ligand that forms.L⁸⁵Not directly and L⁸¹Or L⁸³Bonding, but pass through metal bonding.Ligancy and part number are no more than the ligancy of metal.

n⁸¹Represent 0 to 5.Work as M⁸¹Be when to have ligancy be 4 metal, n⁸¹Be 1 and L⁸⁵It is monodentate ligand.Work as M⁸¹Be when to have ligancy be 6 metal, n⁸¹Preferably 1 to 3, be more preferably 1 or 3, further preferably 1.Work as M⁸¹Be that to have ligancy be 6 metal and n⁸¹Be 1 o'clock, L⁸⁵It is terdentate ligand.Work as M⁸¹Be that to have ligancy be 6 metal and n⁸¹Be 2 o'clock, L⁸⁵Be monodentate ligand and bidentate ligand.Work as M⁸¹Be that to have ligancy be 6 metal and n⁸¹Be 3, L⁸⁵It is monodentate ligand.Work as M⁸¹Be when to have ligancy be 8 metal, n⁸¹Preferably 1 to 5, be more preferably 1 or 2, further preferably 1.Work as M⁸¹Be that to have ligancy be 8 metal and n⁸¹Be 1 o'clock, L⁸⁵It is quinquidentate ligand; Work as n⁸¹Be 2 o'clock, L⁸⁵Be terdentate ligand and bidentate ligand; Work as n⁸¹Be 3 o'clock, L⁸⁵Be a terdentate ligand and two monodentate ligands, or two bidentate ligands and a monodentate ligand; Work as n⁸¹Be 4 o'clock, L⁸⁵Be a bidentate ligand and three monodentate ligands; Work as n⁸¹Be 5 o'clock, L⁸⁵Be five monodentate ligands.Work as n⁸¹Be 2 or when bigger, a plurality of L⁸⁵Can be same to each other or different to each other.

By the preferred implementation of the compound of formula (8) representative is L in the formula (8)⁸¹, L⁸²And L⁸³Represent separately by carbon atom and M⁸¹The aromatic carbocyclic of coordination or heterocycle, or by nitrogen-atoms and M⁸¹The nitrogen heterocyclic ring of coordination, prerequisite are L⁸¹, L⁸²And L⁸³At least one be described nitrogen heterocyclic ring.By carbon atom and M⁸¹The aromatic carbocyclic of coordination or heterocycle and by nitrogen-atoms and M⁸¹Cited carbon atom and the M of passing through in the nitrogenous heterocyclic example of coordination and the formula (1)¹¹The part of coordination and by nitrogen-atoms and M¹¹The example of the part of coordination is identical, has identical preferable range.Y⁸¹And Y⁸²Preferably singly-bound or methylene separately.

By other preferred implementation of the compound of formula (8) representative is by those of formula (13) or (14) representative.

Formula (13)

Formula (14)

Next, the compound of being represented by formula (13) is described.

M⁹¹Have and aforementioned M⁸¹Identical implication and identical preferable range.

Q⁹¹And Q⁹²Representative formation nitrogen heterocyclic ring (contains and M separately⁹¹The ring of the nitrogen-atoms of coordination) group.To by Q⁹¹Or Q⁹²The nitrogen heterocyclic ring that forms has no particular limits, but pyridine preferably, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, pyrazoles, imidazoles, or triazole ring, or contain arbitrarily the condensed ring of these rings (for example quinoline, benzoxazole, benzimidazole and indolenine ring); Or the dynamic isomer of these rings arbitrarily.

By Q⁹¹Or Q⁹²The nitrogen heterocyclic ring that forms is pyridine preferably, pyrazoles, thiazole, imidazoles, or pyrrole ring, or contain arbitrarily the condensed ring of these rings (quinoline for example, benzothiazole, benzimidazole and indolenine ring), or the dynamic isomer of these rings arbitrarily, being more preferably is pyridine or pyrrole ring, or contains the arbitrarily condensed ring (for example quinoline ring) of these rings, or the dynamic isomer of these rings arbitrarily, further pyridine ring and contain the condensed ring of pyridine ring, especially preferred pyridine ring preferably.

Q⁹³Representative forms nitrogen heterocyclic ring and (contains and M⁹¹The ring of the nitrogen-atoms of coordination) group.To by Q⁹³The nitrogen heterocyclic ring that forms has no particular limits, but pyrroles's dynamic isomer preferably, imidazoles or triazole ring, perhaps contain the condensed ring (for example benzopyrrole ring) of these rings arbitrarily, being more preferably is the dynamic isomer of pyrrole ring, or contains the dynamic isomer (for example benzopyrrole ring) of the condensed ring of pyrrole ring.

W⁹¹And W⁹²Have separately and aforementioned W⁵¹And W⁵²Identical implication and identical preferable range.

L⁹⁵Have and aforementioned L⁸⁵Identical implication and identical preferable range.

n⁹¹Have and aforementioned n⁸¹Identical implication and identical preferable range.

Next, the compound of being represented by formula (14) is described.

M¹⁰¹Have and aforementioned M⁸¹Identical implication and identical preferable range.

Q¹⁰²Have and aforementioned Q²¹Identical implication and identical preferable range.

Q¹⁰¹Have and aforementioned Q⁹¹Identical implication and identical preferable range.

Q¹⁰³Representative forms the group of aromatic ring.To by Q¹⁰³The aromatic ring that forms has no particular limits, but benzene preferably, furans, and thiophene, or pyrrole ring or contain the condensed ring (for example naphthalene nucleus) of these rings arbitrarily, being more preferably is phenyl ring or the condensed ring that contains phenyl ring (for example naphthalene nucleus), especially preferably phenyl ring.

Y¹⁰¹And Y¹⁰²Have separately and aforementioned Y²²Identical implication and identical preferable range.

L¹⁰⁵Have and aforementioned L⁸⁵Identical implication and identical preferable range.

n¹⁰¹Have and aforementioned n⁸¹Identical implication and identical preferable range.

X¹⁰¹Have and aforementioned X²¹Identical implication and identical preferable range.

Compound of the present invention can be a low molecular compound, or the weight average molecular weight that oligomer or have calculates with polystyrene is 1,000-5,000, the polymer of 000 scope is more preferably at 2,000-1,000,000 scope, further preferably 3,000-100,000 scope.With respect to polymer, by the structure example of formula (1) representative as in the main chain that can be included in polymer, perhaps in the side chain of polymer.In addition, polymer can be homopolymers or copolymer.Compound of the present invention is low molecular compound preferably.

Another preferred implementation with metal complex of tridentate ligand of the present invention is the metal complex by formula (X1) representative.In metal complex,, be more preferably metal complex by formula (X3) representative preferably by the metal complex of formula (X2) representative by formula (X1) representative.

Next, the compound of being represented by formula (X1) is described.

M^X1Representation metal ion.This metal ion is had no particular limits, but preferably monovalence is to trivalent metal ion, being more preferably is divalence or trivalent metal ion, further preferred trivalent metal ion.Concrete preferred platinum, iridium, rhenium, palladium, rhodium, ruthenium, copper, europium, gadolinium, and terbium ion.Wherein be more preferably platinum, iridium, and europium ion, further preferred platinum and iridium ion, especially preferred iridium ion.

Q^X11, Q^X12, Q^X13, Q^X14, Q^X15And Q^X16Represent separately and M^X1The atom of coordination or have and M^X1The atomic group of the atom of coordination.Work as Q^X11, Q^X12, Q^X13, Q^X14, Q^X15Or Q^X16Representative and M^X1The atomic time of coordination, its instantiation comprises carbon atom, nitrogen-atoms, oxygen atom, silicon atom, phosphorus atoms, and sulphur atom; Preferred this atom is a nitrogen-atoms, oxygen atom, and sulphur atom, or phosphorus atoms, and being more preferably is nitrogen-atoms or oxygen atom.

Work as Q^{X 11}, Q^X12, Q^X13, Q^X14, Q^X15Or Q^X16Representative has and M^X1During the atomic group of the atom of coordination, through carbon atom and M^X1The instantiation of the atomic group of coordination comprises imino group, aromatic hydrocarbon cyclic group (for example benzene, naphthalene), heterocyclic group (for example thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, azoles, pyrroles, imidazoles, pyrazoles, triazole), contain the condensed ring of these rings arbitrarily and the dynamic isomer of these rings arbitrarily.

Through nitrogen-atoms and M^X1The instantiation of the atomic group of coordination comprises nitrogen heterocyclic ring group (pyridine for example; pyrazine; pyrimidine; pyridazine; triazine; thiazole; azoles; the pyrroles; imidazoles; pyrazoles; triazole); it is amino that (for example alkyl amino (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-10 carbon atom; methylamino for example); virtue amino (for example phenyl amino); acylamino-(preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; those of preferred especially 2-10 carbon atom; acetylamino for example; benzamido); alkoxycarbonyl amino (preferably has 2-30 carbon atom; more preferably have 2-20 carbon atom; especially preferably have those of 2-12 carbon atom; methoxycarbonyl amino for example); aryloxycarbonyl amino (preferably has 7-30 carbon atom; more preferably have 7-20 carbon atom, especially preferably have those of 7-12 carbon atom, for example phenyloxycarbonyl amino); sulfuryl amino (preferably has 1-30 carbon atom; more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, for example sulfonyl methane amino; and imino group benzenesulfonamido-).These groups can also be substituted base and replace.

Through oxygen atom and M^X1The instantiation of the atomic group of coordination comprises that alkoxyl (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-10 carbon atom, methoxyl group for example, ethyoxyl, butoxy, the 2-ethyl hexyl oxy), aryloxy group (preferably has 6-30 carbon atom, more preferably have 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, phenoxy group for example, 1-naphthoxy, the 2-naphthoxy), heterocyclic oxy group (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridine oxygen base for example, pyrazoles oxygen base, 2-pyrimidinyl oxy, quinoline oxy), acyloxy (preferably has 2-30 carbon atom, more preferably have 2-20 carbon atom, especially preferably have those of 2-10 carbon atom, for example acetoxyl group, benzoyloxy), silyloxy (preferably has 3-40 carbon atom, more preferably has 3-30 carbon atom, especially preferably have those of 3-24 carbon atom, trimethyl silyloxy for example, the triphenyl silyloxy), carbonyl (ketone group for example, ester group, amide groups), and ether (for example dialkyl group ether, diaryl ether, furyl).

Through sulphur atom and M^X1The instantiation of the atomic group of coordination comprises that alkyl thio-base (preferably has 1-30 carbon atom, more preferably have 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, methyl mercapto for example, ethylmercapto group), arylthio (preferably has 6-30 carbon atom, more preferably has 6-20 carbon atom, especially preferably have those of 6-12 carbon atom, thiophenyl for example), the heterocycle sulfenyl (preferably has 1-30 carbon atom, more preferably has 1-20 carbon atom, especially preferably have those of 1-12 carbon atom, pyridine sulfenyl for example, 2-benzimidazole sulfenyl, 2-benzoxazole sulfenyl, the 2-[4-morpholinodithio sulfenyl), thiocarbonyl (for example thioketones base, thioester), and thioether group (dialkyl sulfide base for example, the diaryl sulfide base, the sulphur furyl).

Through phosphorus atoms and M^X1The instantiation of the atomic group of coordination comprises the dialkyl group phosphino-, diarylphosphino, trialkyl phosphino-, triaryl phosphino-, phosphino-.These groups can also be substituted.

As by Q^X11, Q^X12, Q^X13, Q^X14, Q^X15Or Q^X16The atomic group of representative, preferably pass through the aromatic hydrocarbon cyclic group of carbon atom coordination, by the aromatic heterocyclic group of carbon atom coordination, by the nitrogenous aromatic heterocyclic group of nitrogen-atoms coordination, alkoxy grp, aryloxy group, alkane thio group, arylthio group, the dialkyl group phosphino-, be more preferably aromatic hydrocarbon cyclic group, by the aromatic heterocyclic group and the nitrogenous aromatic heterocyclic group of carbon atom coordination by the carbon atom coordination.

L^X11, L^X12, L^X13And L^X14Represent singly-bound separately, two keys or linking group.Linking group is not particularly limited.The preferred embodiment of linking group comprises and contains carbon, nitrogen, oxygen, arbitrary linking group of sulphur and silicon atom.The instantiation of linking group is as follows, but the present invention is not limited to this.

These linking groups can also be substituted base and replace.Described substituent example comprises in the formula (2) by R²¹To R²⁴Those that the substituting group of representative is explained, and have identical preferable range.As L^X11, L^X12, L^X13Or L^X14, singly-bound preferably, dimethylated methylene base, dimethylated methylene silylation.

Being more preferably by the metal complex of formula (X1) representative is metal complex by formula (X2) representative.Next, the metal complex of being represented by formula (X2) is described.

M^X2Have with aforementioned formula (X1) in M^X1Identical implication and identical preferable range.Y^X21, Y^X22, Y^X23, Y^X24, Y^X25And Y^X26Represent separately and M^X2The atom of coordination.Y^X21And M^X2Between key, Y^X22And M^X2Between key, Y^X23And M^X2Between key, Y^X24And M^X2Between key, Y^X25And M^X2Between key, and Y^X26And M^X2Between key each coordinate bond or covalent bond naturally.Y^X21, Y^X22, Y^X23, Y^X24, Y^X25Or Y^X26Instantiation comprise carbon atom, nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, and silicon atom are more preferably carbon atom and nitrogen-atoms.Each Q^X21, Q^X22, Q^X23, Q^X24, Q^X25And Q^X26Represent necessary atomic group with respectively with each Y^X21, Y^X22, Y^X23, Y^X24, Y^X25And Y^X26Form aromatic hydrocarbon ring or aromatic heterocycle.The aromatic hydrocarbon ring that is formed by these groups or the instantiation of aromatic heterocycle comprise benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrroles, pyrazoles, imidazoles, triazole, azoles, thiazole ， oxadiazole, thiadiazoles, thiophene, and furan nucleus.Benzene preferably, pyridine, pyrazine, pyrimidine, pyrazoles, imidazoles, and triazole ring, being more preferably is benzene, pyridine, pyrazine, pyrazoles, and triazole ring, especially preferred benzene and pyridine ring.These rings can also comprise condensed ring, maybe can also have substituting group.

L^X21, L^X22, L^X23And L^X24Have with aforementioned formula (X1) in L^X11, L^X12, L^X13And L^X14Identical implication and identical preferable range.

By the metal complex of formula (X1) representative further preferably by the metal complex of formula (X3) representative.Next, the metal complex of being represented by formula (X3) is described.

M^X3Have with aforementioned formula (X1) in M^X1Identical implication and identical preferable range.Y^X31, Y^X32, Y^X33, Y^X34, Y^X35And Y^X36Represent separately and M^X3The atom of coordination.Y^X31And M^X3Between key, Y^X32And M^X3Between key, Y^X33And M^X3Between key, Y^X34And M^X3Between key, YX³⁵And M^X3Between key, and YX³⁶And M^X3Between key each coordinate bond or covalent bond naturally.Y^X31, Y^X32, Y^X33, Y^X34, Y^X35Or Y^X36Instantiation comprise carbon atom, nitrogen-atoms, and phosphorus atoms, preferably carbon atom and nitrogen-atoms.L^X31, L^X32, L^X33And L^X34Have with aforementioned formula (X1) in L^X11, L^X12, L^X13And L^X14Identical implication and identical preferable range.

The instantiation of compound of the present invention is as follows, but the present invention is not limited to these compounds.

(synthetic method of metal complex of the present invention)

Metal complex of the present invention (promptly by formula (1) to (14) and formula (X1) compound to (X3) arbitrary representative) can be synthetic by the whole bag of tricks.

For example, described compound can obtain by the following method, at solvent (halogen-kind solvent for example, alcohol-kind solvent, ether-kind solvent, ester-kind solvent, ketone-kind solvent, nitrile-kind solvent, acid amides-kind solvent, sulfone-kind solvent, sulfoxide-kind solvent and water) exist down, perhaps there not being solvent at alkali (various inorganic or organic bases, for example sodium methoxide, potassium tert-butoxide, triethylamine and potash) existence under, perhaps there not being alkali under room temperature or lower temperature, perhaps by heating (except that common heating, heating means by microwave also are effective), part or its dissociating product metallizing thing are reacted.

The activity of the synthetic applied reaction time of metal complex of the present invention according to raw material changes, and the reaction time is had no particular limits, but the preferred reaction time is from 1 minute to 5 days, more preferably from 5 minutes to 3 days, further preferably from 10 minutes to 1 day.

The synthetic applied reaction temperature of metal complex of the present invention changes according to reactivity, reaction temperature is had no particular limits, but preferred reaction temperature is from 0-300 ℃, more preferably from 5-250 ℃, more preferably from 10-200 ℃.

Metal complex of the present invention, as by formula (1) to (14) and formula (X1) compound to (X3) arbitrary representative, the part of part-structure that can be by selecting to form the target complex compound suitably synthesizes.For example, compound by formula (3) representative can followingly synthesize, with part as 6,6 '-two (2-hydroxy phenyls)-2, (part is as 2 for 2 '-bipyridine or derivatives thereof, 9-two (2-hydroxy phenyl)-1,10-phenanthroline, 2,9-two (2-hydroxy phenyl)-4,7-diphenyl-1,10-phenanthroline and 6,6 '-two (2-hydroxyls-5-tert-butyl-phenyl)-2,2 '-bipyridine) to be preferably 0.1-10,0.3-6 more preferably, more preferably the equivalents of 0.5-4 is added into respectively in the metallic compound, identical by described in aforementioned the synthesizing of applied reaction time in the synthetic method of the compound of formula (3) representative and reaction temperature and metal complex of the present invention.

6,6 '-two (2-hydroxy phenyls)-2, the derivative of 2 '-bipyridine ligand can be synthetic by various known methods.For example with 2,2 '-dipyridyl derivatives (for example 1,10-phenanthroline) and methyl phenyl ethers anisole derivative (for example 4-fluoroanisole) are according to Journal of Organic Chemistry, and the method described in 741,11 (1946) is reacted.Perhaps with 2 of halogenation; 2 '-dipyridyl derivatives (for example 2; 9-two bromo-1; the 10-phenanthroline) and 2-anisyl boronic acid derivatives (for example 2-methoxyl group-5-fluorophenyl boric acid) carry out the Suzuki coupling reaction as initiation material; pass through then according to Journal ofOrganic Chemistry, the method described in 741,11 (1946); or in the presence of pyridine hydrochloride, add the method for thermal reaction mixture, methyl is discharged as blocking group.Perhaps; can be with 2; 2 '-bipyridine boronic acid derivatives (for example 6; 6 '-two (4; 4; 5; 5-tetramethyl-1,3,2-dioxy borine (dioxaborolyl)-2; 2 '-bipyridine) and the methyl phenyl ethers anisole derivative of halogenation (for example 2-bromoanisole) carry out the Suzuki coupling reaction as initiation material; pass through then according to Journal ofOrganic Chemistry, the method described in 741,11 (1946); or in the presence of pyridine hydrochloride, add the method for thermal reaction mixture, methyl is discharged as blocking group.

The light-emitting device that comprises metal complex of the present invention is described below.

To light-emitting device of the present invention for example their system, driving method and type of service have no particular limits, as long as wherein use metal complex of the present invention.As typical light-emitting device, what can mention is organic EL (electroluminescence) device.

El light emitting device of the present invention is the Organnic electroluminescent device that comprises pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes.Described organic layer preferably comprises hole transmission layer and luminescent layer, further preferably at least one deck be to be selected from exciton barrier-layer, hole injection layer, the layer of hole blocking layer and electron transfer layer.

El light emitting device of the present invention preferably has the layer of inclusion compound between negative pole and luminescent layer, the ionization potential of described compound is 5.9eV or higher (6.0eV or higher more preferably); More preferably, having ionization potential is 5.9eV or higher electron transfer layer.

Formation method for the organic layer of the light-emitting device that comprises metal complex of the present invention has no particular limits.As described method, can adopt the whole bag of tricks, as the vapor deposition method of resistance heating, electronic beam method, sputtering method, molecular layer is legal, rubbing method (as, spraying process, dip coating, infusion process, rolling method, intaglio plate rubbing method, oppositely rubbing method, roller brush method, airblade coating method, curtain coating method, spin-coating method, flow coat method, rod is coated with method, miniature intaglio plate rubbing method, gas scraper rubbing method, blade rubbing method, the extrusion coated method, transferring roller rubbing method, contact rubbing method, the curtain coating rubbing method, extrusion coated method, excellent rubbing method and screen cloth rubbing method wind the line), ink-jet method, print process, and transfer method.Consider characteristic and production, vapor deposition method, rubbing method and the transfer method of preferred resistance heating.

Described positive pole provides the hole to hole injection layer, hole transmission layer, and luminescent layer, or the like; And can use metal for this reason, alloy, metal oxide, conductive compound, or the mixture of these materials preferably use work content to be 4eV or bigger material at this.The object lesson of described material comprises: conducting metal oxide, and as tin oxide, zinc oxide, indium oxide, and tin indium oxide (ITO); Metal, as gold, silver, chromium, and nickel; The mixture of these metals and conducting metal oxide or laminated thing; The inorganic conductive material is as cupric iodide and copper sulfide; The organic conductive material, as polyaniline, polythiophene, and polypyrrole; And the laminated thing of these materials and ITO.Consider productibility, high conductivity and transparency are preferably used conducting metal oxide, especially preferably use ITO.Anodal film thickness can be selected arbitrarily according to material therefor, but its thickness is usually preferably from 10 nanometers to 5 micron, is more preferably from 50 nanometers to 1 micron, more preferably from 100 nanometer to 500 nanometers.

Described positive pole is generally comprised within one or more layers that forms on soda-lime glass, alkali-free glass or the transparent resin matrix.When using glass matrix,, preferably use alkali-free glass in order to reduce the wash-out of ion from glass.In addition, when using soda-lime glass, preferably provide barrier coat such as silicon dioxide.As long as described matrix can keep enough mechanical strengths, its thickness is had no particular limits.When using glass, described thickness is generally 0.2 millimeter or bigger, preferred 0.7 millimeter or bigger.

According to the described positive pole of employed material preparation the time, can make and in all sorts of ways.Utilizing under the situation of ITO, for example, by electronic beam method, sputtering method, the resistance heating vapor deposition method, chemical reaction method (for example, sol-gel process), or the method for coating tin indium oxide dispersion forms one or more layers film.

Method by as positive pole is washed might reduce the driving voltage of device or element or increase its luminous efficacy.Under the situation of using ITO, for example UV-ozone treatment or plasma treatment are effective.

Described negative pole offers electron injecting layer with electronics, electron transfer layer, and luminescent layer etc., and consider negative pole and its adjacent layer such as electron injecting layer, and electron transfer layer, or the adhesion strength of luminescent layer, ionization potential and stability wait selects negative pole.As the material of negative pole, can use metal, alloy, metal halide, metal oxide, conductive compound, or these mixtures of material.Concrete example comprises: alkali metal (for example, lithium, sodium, potassium) or its fluoride or oxide, alkaline-earth metal (for example magnesium, calcium) or its fluoride or oxide, gold, silver, lead, aluminium, sodium-potassium-sodium alloy or its hybrid metal, lithium-aluminium alloy or its hybrid metal, magnesium-silver alloy or its hybrid metal, and rare earth metal, as indium, ytterbium or the like; Preferred work content is 4eV or littler material, more preferably aluminium, lithium-aluminium alloy or its hybrid metal, and magnesium-silver alloy or its hybrid metal.Negative pole structure not only can be the individual layer of above-claimed cpd or its mixture, but also can be the laminated thing that comprises above-claimed cpd or its mixture.For example, preferred aluminium/lithium fluoride, or the laminated thing of aluminium/lithia.The thickness of negative pole can be selected arbitrarily according to material therefor, but its thickness is usually preferably from 10 nanometers to 5 micron, is more preferably from 50 nanometers to 1 micron, more preferably from 100 nanometers to 1 micron.

Operable method such as electronic beam method when making negative pole, sputtering method, the resistance heating vapor deposition method, rubbing method, and transfer method can the single metals of gas deposition or two or more components of gas deposition simultaneously.In addition, simultaneously the multiple metal of gas deposition to be forming alloy electrode, but the perhaps pre-prepd alloy of gas deposition.

Preferably, film resistor (sheet resistance) anodal and negative pole is lower, is preferably hundreds of Ω/ or lower.

The material that is used for luminescent layer can be following material, it can cambium layer, described layer can rise when both having accepted when it applies electric field by positive pole, and hole injection layer or hole transmission layer injected holes can be accepted again by negative pole, electron injecting layer or electron transfer layer injected electrons; Injection electric charge is wherein shifted; Perhaps by reconfiguring to hole and electronics the position is provided and can be luminous.Except that compound of the present invention, described examples of material comprises: various metal complexs, and typical example is the metal complex or the rare-earth complex benzoxazole derivative of following material, benzimidizole derivatives, benzothiazole derivant, the styryl benzene derivative, the polyphenyl derivative, diphenyl diethylene derivative, tetraphenylbutadiene derivative, naphthalimide derivative, coumarin derivative ， perylene derivative, perinone derivative oxadiazole derivative, the aldazine derivative, pyraridine derivative, cyclopentadiene derivant, the diphenylethyllene anthracene derivant, quinacridone derivative, Pyrrolopyridine derivatives, thiadiazoles pyridine derivate, cyclopentadiene derivant, the styrylamine derivative, aromatics two methylidyne compounds and oxine derivative; Polymer, as polythiophene, polyphenylene, and polyphenylene vinylene; Organosilan; Transition metal complex (for example, triphenyl pyridine iridium and porphyrin platinum, and derivative).

Material of main part as luminescent layer, preferably cited amines (for example triarylamine compound), the accurate oxide of metal-chelating (metal chelate oxynoid compounds) (compound) with metal-oxygen key, wherein said metal is an aluminium, zinc or transition metal, with part be the oxine derivative, 2-(2-pyridine radicals) phenol derivatives etc., poly (arylene ether) compound (for example hexaphenyl benzene derivative), fused aromatic carbocyclic compound and non-complexing aromatics nitrogen-containing heterocycle compound (for example carbazole derivates).The material of main part of described luminescent layer can be the mixture of at least two kinds of compounds.

Thickness to luminescent layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.

Although the method that forms luminescent layer is had no particular limits, can use as the resistance heating vapor deposition method, electronic beam method, sputtering method, molecular layer is legal, rubbing method, ink-jet method, print process, LB (Langmuir-Blodgett) facture, and transfer method.Preferably resistance heating vapor deposition method and rubbing method.

Luminescent layer can be formed by the unification compound, or is formed by two or more compounds.In addition, luminescent layer can have single layer structure, or the sandwich construction of two-layer at least composition.Each layer can be launched the light of different color, and therefore, luminescent layer can be launched for example white light.Single luminescent layer can be launched white light.When luminescent layer was multilayer, each layer can be formed by homogenous material, or formed by at least two kinds of compounds or material.

If the material of hole injection layer and hole transmission layer has (1) from anodal injected hole, (2) transporting holes and (3) stop that described material is enough by any of these three kinds of effects of negative pole injected electrons.The object lesson of described material comprises: carbazole derivates, triazole derivative, Zole derivatives oxadiazole derivative, imdazole derivatives, poly-aryl alkane derivatives, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, aryl amine derivatives, the chalcone derivative of amino-replacement, styryl anthracene derivant, fluorenone derivatives, hydazone derivative, stilbene derivatives, the silazane derivative, the aromatic uncle amine compound, styrylamine compound, aromatics two methine compounds, porphyrins, the polysilanes compound, poly-(N-vinylcarbazole) derivative, phenyl amines copolymer, the conducting polymer weight oligomers is as thiophene oligomers and polythiophene; Organic silane compound, carbon film, and compound of the present invention.Thickness to hole injection layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.Thickness to hole transmission layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.Hole injection layer or hole transmission layer can have the single layer structure of one or both or multiple above-mentioned material, perhaps can be the sandwich constructions that comprises multilayer, and described multilayer has identical or different component.

As the material of hole injection layer, preferably copper phthalocyanine and star burst type (star-burst type) amines.

The example of the formation method of hole injection layer and hole transmission layer comprises: vacuum deposition method, the LB method is with the method that above-mentioned hole injection/transferring material is dissolved or dispersed in solvent and is coated with, ink-jet method, print process, and transfer method.Under the situation of rubbing method, hole injection/transferring material usable resins component is dissolved or is disperseed.The example of described resin Composition comprises: polyvinyl chloride, Merlon, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfones, polyphenylene oxide, polybutadiene, poly-(N-vinylcarbazole), hydrocarbon resins, ketone resins, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melmac, unsaturated polyester resin, alkyd resins, epoxy resin, silicones, or the like.

Inject electronics if the material of electron injecting layer and electron transfer layer has (1) from negative pole, (2) transmission electronic and (3) stop (as the barrier layer) by any of these three kinds of effects of anodal injected holes, and described material is enough.As the material of electron transfer layer, the accurate oxide of preferable alloy chelating, the aromatic heterocycle compounds of fused aromatic carbocyclic compound and non-complexing.The instantiation of described material comprises triazole derivative, Zole derivatives oxadiazole derivative, imdazole derivatives, fluorenone derivatives, anthraquinone bismethane (anthraquinodimethane) derivative, anthracyclinone derivatives, the diphenyl quinone derivative, the thiapyran dioxide derivative, carbodiimide derivative, fluorenylidene methane Derivatives, the diphenylethyllene pyrazines derivatives, aromatic ring such as naphthalene nucleus be with the tetracarboxylic anhydride of perylene, and phthalocyanine derivates is by the various metal complexs of the metal complex representative of oxine derivative, metal phthalocyanine and metal complex with benzoxazole or benzothiazole part, organic silane compound.Thickness to electron injecting layer and electron transfer layer has no particular limits, but its thickness is usually preferably from 1 nanometer to 5 micron, is more preferably from 5 nanometers to 1 micron, more preferably from 10 nanometer to 500 nanometers.Electron injecting layer and electron transfer layer can be the single layer structures that comprises one or both or multiple above-mentioned material, perhaps can be the sandwich constructions that comprises multilayer, and described multilayer has identical or different component.

The example of the formation method of electron injecting layer and electron transfer layer comprises: vacuum deposition method, the LB method is with the method that above-mentioned hole injection/transferring material is dissolved or dispersed in solvent and is coated with, ink-jet method, print process, and transfer method.Under the situation of rubbing method, electronics injection/transferring material usable resins component is dissolved or is disperseed.As resin Composition, for example can use those components of in hole injection layer and hole transmission layer, enumerating.

Make the material of device or element accelerated ageing such as the function in water or oxygen access to plant or the element if protective layer has to stop, this protective layer material enough.The object lesson of described material comprises as In, Sn, Pb, Au, Cu, Ag, Al, Ti and Ni; Metal oxide, as MgO, SiO, SiO₂, Al₂O₃, GeO, NiO, CaO, BaO, Fe₂O₃, Y₂O₃And TiO₂Metal fluoride is as MgF₂, LiF, AlF₃And CaF₂Metal nitride is as SiN_xAnd SiO_xN_yPolyethylene, polypropylene, polymethyl methacrylate, polyimides, polyureas, polytetrafluoroethylene, polychlorotrifluoroethylene, poly-dichloro difluoroethylene, the copolymer of chlorotrifluoroethylene and dichloro difluoroethylene, the copolymer that the monomer mixture copolymerization of tetrafluoroethene and at least a comonomer makes, the fluorinated copolymer that on main chain, has circulus, water absorption rate is at least 1% absorbent material, and water absorption rate is at most 0.1% water-repellent substance.

Formation method to protective layer also has no particular limits, and for example can adopt vacuum deposition method, sputtering method; reactive sputtering, MBE (molecular beam epitaxy) method, ion beam method; ion-plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD (chemical vapor deposition) method; the laser CVD method; add the hot CVD method, source of the gas CVD method, rubbing method; print process, and transfer method.

Embodiment

Explain the present invention in more detail referring now to following embodiment, but should be understood that, implement concrete scheme of the present invention and be not construed as limiting the invention.

Synthesizing of compound (1)

To 6,6 '-two (2-hydroxy phenyls)-2,2 '-bipyridine (0.1g) and PtCl₂Add benzonitrile (10ml) (0.16g), then reflux 3 hours under nitrogen atmosphere.After reaction solution is cooled to room temperature, methyl alcohol is added to forms precipitation in the reaction solution, suction strainer should precipitation.Institute's solid that obtains obtains 0.06g compound (1) with silica gel chromatography (chloroform is as developer) purifying.Structure with mass spectrography authenticating compound (1).The UV irradiation contains the chloroformic solution of compound (1) under nitrogen atmosphere, obtains reddish orange emission light (λ_Max=624nm).

As 6,6 '-two (2-hydroxy phenyls)-2 of initiation material, 2 '-bipyridine can be according to Journal of Organic Chemistry in above-mentioned reaction, and the method described in 741,11 (1946) is synthetic.Perhaps this compound can be synthetic by following proposal.

Synthetic 6,6 '-two (2-methoxyphenyls)-2,2 '-bipyridine

To 6,6 '-two bromo-2,2 '-bipyridine (1.15g), 2-methoxybenzene ylboronic acid (1.45g), PPh₃(0.167g), potash (2.2g) and P_d(OAc)₂Add dimethoxy-ethane (10ml) and water (10ml) in the mixture (36mg), then reflux 4 hours under nitrogen atmosphere.After reaction solution is cooled to room temperature, chloroform (20ml) is added in the reaction solution with water (20ml) separates.Concentrate organic layer then.Carry out purifying with silica gel chromatography (chloroform is as developer), obtain 0.9g 6,6 '-two (2-methoxyphenyl)-2,2 '-bipyridine.

Synthetic 6,6 '-two (2-hydroxy phenyls)-2,2 '-bipyridine

At nitrogen atmosphere, 160 ℃ of following heating 6,6 '-two (2-methoxyphenyls)-2,2 '-bipyridine ligands (0.3g), and the mixture of pyridine hydrochloride (10g) 4 hours.After reaction solution is cooled to room temperature, chloroform (20ml) is added in the reaction solution with water (20ml) separates.Concentrate organic layer then.Carry out purifying with silica gel chromatography (chloroform is as developer), obtain 0.2g6,6 '-two (2-hydroxy phenyls)-2,2 '-bipyridine.

Synthetic schemes according to synthetic compound (79) of above-mentioned same procedure and compound (88) is as follows.

The λ of the light of the compound in dichloroethanes (79) emission_MaxBe 512nm, and the λ of the light of the compound in dichloroethanes (88) emission_MaxBe 620nm.

By the compound of formula (11) or (12) representative, each alkyl naturally of substituting group wherein, aryl, heteroaryl or halogen atom also can be synthetic according to said method.

Comparative Examples 1

The ITO substrate of cleaning is placed cold boiler, and evaporation TPD (N, N-diphenyl-N, N-two (tolyl) benzidine) formation has the film that thickness is 50nm on this substrate, coevaporation PtOEP (octaethylporphyrin platinum complex) and compd A (weight ratio is 1: 17) have the film that thickness is 36nm with formation then, evaporate compd A afterwards and have the film that thickness is 36nm with formation.Then, patterned mask (patterned mask) (each emitting area is adjusted to 4mmx5mm) is set on the organic thin layer of Huo Deing in the above, and in cold boiler, further evaporates lithium fluoride, have the film that thickness is 3nm thereon thereby form; And then the thick aluminium film of deposition 400nm.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measurement mechanism (Model 2400 (trade name)) that Ltd. makes makes the EL device of producing thus luminous; And the photometer BM-8 (trade name) that utilizes Topcon Co. to make measures the brightness that the EL device demonstrates.As the result who measures, find that the emission brightness of being sent by the EL device is 200cd/m², its external quantum efficiency is 1.1%, and high-high brightness is 390cd/m²

Embodiment 1

The ITO substrate of cleaning is placed cold boiler, and evaporation TPD (N, N-diphenyl-N, N-two (tolyl) benzidine) formation has the film that thickness is 50nm on this substrate, coevaporation has the film that thickness is 36nm according to compound of the present invention (1) and compd A (weight ratio is 1: 17) with formation then, evaporates compd B afterwards and has the film that thickness is 36nm with formation.Then, patterned mask (each emitting area is adjusted to 4mmx5mm) is set on the organic thin layer of Huo Deing in the above, and in cold boiler, further evaporates lithium fluoride, have the film that thickness is 3nm thereon thereby form; And then the thick aluminium film of deposition 400nm.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measurement mechanism (Model 2400 (trade name)) that Ltd. makes makes the EL device of producing thus luminous; And the photometer BM-8 (trade name) that utilizes Topcon Co. to make measures the brightness that the EL device demonstrates.As the result who measures, find that the emission brightness of being sent by the EL device is 200cd/m², its external quantum efficiency is 2.8%, and high-high brightness is 1090cd/m²

Embodiment 2

The ITO substrate of cleaning is placed cold boiler, and evaporate TPD (N successively, N-diphenyl-N, N-two (tolyl) benzidine) formation has the film that thickness is 50nm on this substrate, coevaporation has the film that thickness is 36nm according to compound of the present invention (1) and compd A (weight ratio is 1: 2) with formation then, evaporates compd B afterwards and has the film that thickness is 36nm with formation.Then, patterned mask (each emitting area is adjusted to 4mmx5mm) is set on the organic thin layer of Huo Deing in the above, and in cold boiler, further evaporates lithium fluoride, have the film that thickness is 3nm thereon thereby form; And then the thick aluminium film of deposition 400nm.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measurement mechanism (Model 2400 (trade name)) that Ltd. makes makes the EL device of producing thus luminous; And the photometer BM-8 (trade name) that utilizes Topcon Co. to make measures the brightness that the EL device demonstrates.As the result who measures, find that the emission brightness of being sent by the EL device is 200cd/m², its external quantum efficiency is 4.4%, and high-high brightness is 3820cd/m²

Comparative Examples 2

According to U.S. patent No.6,653, the method described in the embodiment 8 of 654B1 prepares EL device (device No-101).

Comparative Examples 3

The ITO substrate of cleaning is placed cold boiler, and evaporation α-NPD forms on this substrate and has the hole transmission layer that thickness is 50nm.Then separately with 0.4nm/sec and 0.02nm/sec coevaporation Bepp as main body₂With as the compound (65) of luminescent material so that thickness is 40nm, form luminescent layer thus.Then, patterned mask (each emitting area is adjusted to 2mmx2mm) is set on the organic thin layer of Huo Deing in the above, and in cold boiler, further evaporates lithium fluoride, have the film that thickness is 1.5nm thereon thereby form; And then the thick aluminium film of deposition 200nm.Then, at this device of sealing after wherein adding drier, with preparation EL device (device No-102).In addition, prepare another EL device (device No-103), just replace described luminescent material with compound (1) as above-mentioned identical mode.

Embodiment 3

Form luminescent layer with the method identical with Comparative Examples 3, just the thickness with main body changes 36nm into.Evaporating compd B then is the electron transfer layer of 36nm to form thickness.Then, patterned mask (each emitting area is adjusted to 2mmx2mm) is set on the organic thin layer of Huo Deing in the above, and in cold boiler, further evaporates lithium fluoride, have the film that thickness is 5nm thereon thereby form; And then the thick aluminium film of deposition 500nm.Then, at this device of sealing after wherein adding drier, with preparation EL device (device No-104).In addition, prepare another EL device (device No-105), just replace described material of main part with compd A as above-mentioned identical mode.

Embodiment 4

The ITO substrate of cleaning is placed cold boiler, and the evaporation copper phthalocyanine is the film of 10nm to form thickness on this substrate, evaporates α-NPD then thereon and have the film that thickness is 20nm, form hole transmission layer thus with formation.Then separately with 0.4nm/sec and 0.02nm/sec coevaporation as the compd A of main body and as the compound (1) of luminescent material so that thickness is 30nm, form luminescent layer thus.On luminescent layer, evaporation BAlq has the hole blocking layer that thickness is 10nm with formation, evaporates Alq afterwards and has the electron transfer layer that thickness is 40nm with formation.Then, patterned mask (each emitting area is adjusted to 2mmx2mm) is set on the organic thin layer of Huo Deing in the above, and in cold boiler, further evaporate lithium fluoride, have film that thickness be 5nm thereby form thereon, and then the thick aluminium film of deposition 500nm.Then, at this device of sealing after wherein adding drier, with preparation EL device (device No-201).In addition, preparing other EL device (device No-202 to 206) as above-mentioned identical mode, is change material of main part as shown in table 2.

Next, the EL device for preparing thus of following evaluation.

By applying dc constant voltage on it, by by Toyo Technica Co., the source measuring mechanism (Model 2400 (trade name)) that Ltd. makes makes EL device of the present invention and comparison luminous; And the photometer BM-8 (trade name) that utilizes Topcon Co. to make measures the brightness that each EL device demonstrates and the spectroanalysis instrument PMA-11 (trade name) that uses Hamamatsu Photonics KK to make measures wavelength of transmitted light to obtain luminous efficiency.Next, following evaluation persistence is at first at 1mA/4mm²Speed under drive this device, measure original intensity.Then, with 1mA/4mm²Speed under after low current drives this device 200h, measure brightness.By the brightness of 200h is compared the conservation rate that obtains brightness with original intensity.The results are shown in table 1 and 2.

The result confirms that the device of the present invention contain electron transfer layer compares with the device in the Comparative Examples, shows the enhanced brightness conservation rate, thereby realizes the persistence of the excellence of this device.In addition, aromatic heterocycle compounds by material of main part being changed into non-complexing such as compd A and further put forward the persistence of this device.

Table 2

The device number	Luminescent material	Material of main part	Emission light λ_max	The brightness conservation rate	Comment
The device number	Luminescent material	Material of main part	Emission light λ_max	The brightness conservation rate	Comment	??201	Compound (1)	Compd A	??615nm	??81％	The present invention
??202	Compound (15)	Compd A	??586nm	??88％	The present invention	??201	Compound (1)	Compd A	??615nm	??81％	The present invention
??202	Compound (15)	Compd A	??586nm	??88％	The present invention	??204	Compound (79)	Compd A	??509nm	??83％	The present invention
??205	Compound (88)	Compd A	??620nm	??79％	The present invention	??204	Compound (79)	Compd A	??509nm	??83％	The present invention
??205	Compound (88)	Compd A	??620nm	??79％	The present invention	??206	Compound (15)	??BAlq	??585nm	??92％	The present invention

Device is formed: ITO/CuPc (10nm)/NPD (20nm)/5 weight % luminescent material-material of main part (30nm)/BAlq (10nm)/Alq (40nm)/LiF-Al

In addition, the result confirms to use copper phthalocyanine (CuPc) further to improve the persistence of this device as hole injection layer and BAlq as hole blocking layer, and compound of the present invention makes the ruddiness of emission and green glow have excellent color purity.And compound of the present invention makes that also radiative wavelength is shorter.

Industrial applicibility

Light-emitting device of the present invention is all very excellent aspect external quantum efficiency and maximum luminousing brightness, and has the excellent characteristics of luminescence (performance).In addition, the persistence of this light-emitting device is also very excellent.Light-emitting device of the present invention preferably is suitable for following field, as display unit, and display, backlight, electrophotography, searchlighting light source, recording light source, exposure light source, reading lamp source, signal, annunciator, interior lighting, and optical communication.In addition, compound of the present invention can be used for electroluminescent device, and medical usage, brightener, photographic material, ultra-violet absorber, laser dye, recording medium material, ink-jet pigment, colour filter dyestuff, color correction filter etc.New complex compound of the present invention is suitable for preparing the light-emitting device of aforesaid excellence.

Although invention has been described in conjunction with embodiment of the present invention, except as otherwise noted, the present invention is not limited to described arbitrary details, and the present invention is limited by the scope of listing in as appended claims in its spirit and scope.

Claims

1. Organnic electroluminescent device, it comprises pair of electrodes and at least one organic layer that comprises luminescent layer between described pair of electrodes, and wherein at least one layer between described pair of electrodes comprises at least a metal complex with three toothed chain structure parts or higher multiple tooth chain structure part.

2. Organnic electroluminescent device as claimed in claim 1, the metal ion in the wherein said metal complex is selected from platinum, iridium, rhenium, palladium, rhodium, ruthenium and copper ion.

3. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex does not have carbon-to-metal bond.

4. as each described Organnic electroluminescent device of claim 1-3, wherein said metal complex is phosphorescent metal complex, and described metal complex is contained in the described luminescent layer.

5. as each described Organnic electroluminescent device of claim 1-4, wherein said metal complex is the compound by formula (1) representative:

Formula (1)

6. as each described Organnic electroluminescent device of claim 1-5, wherein said metal complex is the compound by formula (2) representative:

Formula (2)

7. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each pyridine ring naturally of the ring that forms, and Y²¹The linking group that representative is made up of at least one atom.

8. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each pyridine ring naturally of the ring that forms, and Y²¹Represent singly-bound or two key, and X²¹And X²²Represent sulphur atom or replacement or unsubstituted nitrogen-atoms separately.

9. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each 5 member heterocyclic ring containing nitrogen naturally of the ring that forms.

10. Organnic electroluminescent device as claimed in claim 6, wherein said metal complex are the compounds by formula (2) representative, wherein by Q²¹The ring that forms and by Q²²Each contains 6 yuan of heterocycles of at least two nitrogen-atoms naturally the ring that forms.

11. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex are the compounds by formula (9) representative:

Formula (9)

Wherein, M^A1Representation metal ion; Q^A1And Q^A2Representative forms the atomic group of nitrogen heterocyclic ring necessity separately; R^A1, R^A2, R^A3And R^A4Represent hydrogen atom or substituting group separately; R^A1And R^A2, and R^A3And R^A4Can be respectively each other bonding to form ring; Y^A2And Y^A3Represent linking group or singly-bound separately; Y^A1Represent linking group, singly-bound or two key so that two bidentate ligands in bracket are linked together; L^A5Representative and M^A1The part of coordination; n^A1Represent 0 to 4 integer.

12. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex are the compounds by formula (10) representative,

Formula (10)

13. as each described Organnic electroluminescent device of claim 1-4, wherein said metal complex is the compound by formula (8) representative,

Formula (8)

14. Organnic electroluminescent device as claimed in claim 13, wherein said metal complex are the compound by formula (8) representative, wherein L⁸¹, L⁸²And L⁸³Represent separately by carbon atom and M⁸¹The aromatic carbocyclic of coordination or heterocycle, or by nitrogen-atoms and M⁸¹The nitrogen heterocyclic ring of coordination; And L⁸¹, L⁸²And L⁸³In be described nitrogen heterocyclic ring one of at least.

15. Organnic electroluminescent device as claimed in claim 1 or 2, wherein said metal complex are the compounds by formula (X1) representative:

Formula (X1)

16. Organnic electroluminescent device as claimed in claim 15, wherein said metal complex by formula (X1) representative are the compounds by formula (X2) representative:

Formula (X2)

17. Organnic electroluminescent device as claimed in claim 15, wherein said metal complex by formula (X1) representative are the compounds by formula (X3) representative:

Formula (X3)

18. as each described Organnic electroluminescent device of claim 1-17, wherein said organic layer comprises at least one luminescent layer and hole transmission layer, and described organic layer also comprises the layer that at least one is selected from exciton barrier-layer, hole injection layer, hole blocking layer and electron transfer layer.

19. as each described Organnic electroluminescent device of claim 1-18, wherein said organic layer comprises at least one luminescent layer, and the material of main part of described luminescent layer is selected from amines, the accurate oxide of metal-chelating, wherein said metal is aluminium, zinc or transition metal, polyarylene compound, fused aromatic carbocyclic compound and non-complexing aromatic heterocycle compounds.

20. as each described Organnic electroluminescent device of claim 1-19, wherein said organic layer comprises at least one electron transfer layer, and wherein electron transport material is selected from the accurate oxide of metal-chelating, polyarylene compound, fused aromatic carbocyclic compound and non-complexing aromatic heterocycle compounds.

21. as each described Organnic electroluminescent device of claim 1-20, wherein said organic layer comprises at least one luminescent layer, the material of main part of described luminescent layer is made up of at least two kinds of compounds.

22. compound by formula (11) representative:

Formula (11)

23. compound by formula (12) representative:

Formula (12)

Wherein, R^D3And R^D4Represent hydrogen atom or substituting group separately; R^D1And R^D2Represent substituting group separately; n^D1And n^D2Represent 0 to 4 integer separately; When there being a plurality of R^D1The time, each R^D1Can be same to each other or different to each other, and a plurality of R^D1Bonding is to form ring each other; When there being a plurality of R^D2The time, each R^D2Can be same to each other or different to each other, and a plurality of R^D2Bonding is to form ring each other; Y^D1Representative has vinyl, phenylene, pyridine ring, pyrazine ring, the pyrimidine ring of replacement in 1-and 2-position or has the alkylidene of 1 to 8 carbon atom.