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.2021 May 6;27(26):7383-7390.
doi: 10.1002/chem.202005312. Epub 2021 Mar 15.

New Noncentrosymmetric Tetrel Pnictides Composed of Square-Planar Gold(I) with Peculiar Bonding

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New Noncentrosymmetric Tetrel Pnictides Composed of Square-Planar Gold(I) with Peculiar Bonding

Shannon J Lee et al. Chemistry..

Abstract

Three novel isostructural equiatomic gold tetrel pnictides, AuSiAs, AuGeP, and AuGeAs, were synthesized and characterized. These phases crystallize in the noncentrosymmetric (NCS) monoclinic space group Cc (no. 9), featuring square-planar Au within cis-[AuTt2 Pn2 ] units (Tt=tetrel, Si, Ge; Pn=pnictogen, P, As). This is in drastic contrast to the structure of previously reported AuSiP, which exhibits typical linear coordination of Au with Si and P. Chemical bonding analysis through the electron localization function suggests covalent two-center two-electron Tt-Pn bonds, and three-center Au-Tt-Au and Au-Pn-Au bonds with 1.6 e- per bond. X-ray photoelectron spectroscopy studies support the covalent and nonionic nature of Au-Pn and Au-Tt bonds. The title materials were found to be n-type narrow-gap semiconductors or semimetals, with nearly temperature-independent electrical resistivities and low thermal conductivities. A combination of the semimetallic properties with tunable NCS structure provides opportunities for the development of materials based on gold tetrel pnictides.

Keywords: X-ray photoelectron spectroscopy; electron localization function; gold; noncentrosymmetric structures; tetrel pnictides.

© 2021 The Authors. Published by Wiley-VCH GmbH.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
A comparison of AuSiP and AuGeP (isostructural to AuSiAs and AuGeAs) crystal structures with unit cells outlined in gray. Au: yellow, Si: black, Ge: gray, P: red.
Figure 2
Figure 2
Crystal structure of AuGeP emphasizing the layers of square‐planarcis‐[AuGe2P2] coordination with a) stacking of Au−Ge−P layers, b) top view of one layer with square‐planar units highlighted in gray, c) Ge−P chains throughout the structure, and d) side view of the Ge−P chains. Au: yellow, Ge: gray, P: red.
Figure 3
Figure 3
a) Electronic band structure and b) projected DOS for AuGeP calculated with PBE+SOC. The top valence band in a) is shown in blue.
Figure 4
Figure 4
ELF isosurfaces with variousη values, emphasizing tetrahedral coordination around Ge, P, Si, and As, and slices of the ELF of AuGeP and AuSiAs. Au: yellow, Si: black, Ge: gray, P: red, As: pink.
Figure 5
Figure 5
Basins assigned for a) a unit of square‐planar [AuGe2P2] with the Au core (yellow) basin, corresponding to a total of 78.1 e− plotted with Au−Ge (gray) and Au−P (red) bonding basins with the respective integrations of electrons. b) Three‐centered bond highlighted for Au−Ge−Au (black) and Au−P−Au (red) triangles based on chemical bonding analysis. c) The linear Au−Au−Au chain showing the Au−Ge (gray) basin directly touching two Au core basins (blue and yellow) and the Au−P (red) basin directly touching two Au core basins (yellow and green). d) Local tetrahedral coordination for Ge and P, with three‐centered bonds highlighted (black and red triangles).
Figure 6
Figure 6
Au 4 f, Ge 3 d, and P 2 p XPS spectra for AuGeP before (0 s) and after (20 s) sputtering. Raw data (solid black line), background (black dashed line), and highlighted fit components (red and blue lines) for Au 4 f are shown. Vertical blue dashed lines indicate the signal corresponding to the oxidized surface species, which are reduced or removed after sputtering. Vertical red dashed lines indicate the signals corresponding to the bulk nature of the sample.
Figure 7
Figure 7
AuGeP (black), AuSiAs (red), and AuGeAs (blue) temperature‐dependent transport properties measured from 10 to 280 K for thermal conductivity (left) and Seebeck effect (middle), and 2 to 280 K for electrical resistivity (right).
See this image and copyright information in PMC

References

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