AuPb2I7: A Narrow Bandgap Au3+ Iodide Semiconductor

Grant C.B. Alexander; Douglas H. Fabini; Ram Seshadri; Mercouri G. Kanatzidis

doi:10.1021/acs.inorgchem.7b02723

AuPb₂I₇: A Narrow Bandgap Au³⁺ Iodide Semiconductor

Grant C.B. Alexander, Douglas H. Fabini, Ram Seshadri, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

The unusual Au³⁺ ternary halide AuPb₂I₇ has been isolated from reactions of AuI, PbI₂, and I₂. AuPb₂I₇ crystallizes in the triclinic P1̄ space group as micron-scale needles with cell dimensions a = 4.5170(3) Å, b = 7.3847(4) Å, c = 12.2970(7) Å, α = 76.374(4)°, β = 83.711(4)°, γ = 72.987(3)° at room temperature with p = 6.538 g/cm³ and has no structural phase transition down to 100 K. The title compound has a unique three-dimensional structure composed of [Pb₂I₇]^3- pseudolayers extending in [010] bridged by square planar Au³⁺ at an oblique angle in the [001] direction. The pseudolayers are composed of ¹/_∞[Pb₂I₂]²⁺ chains propagating down [100] linked by square planar I^- ions through [010]. AuPb₂I₇ has a bandgap of 1.17 eV and is stable in air for several days, before degrading to PbI₂, Au⁰, and I₂. Density functional theory calculations show that AuPb₂I₇ is an indirect bandgap semiconductor where the bandgap stems predominantly from Au-I metal-ligand charge transfer.

Original language	English (US)
Pages (from-to)	804-810
Number of pages	7
Journal	Inorganic chemistry
Volume	57
Issue number	2
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02723
State	Published - Jan 16 2018

Funding

Optical Absorption and Electronic Structure. The bandgap of black AuPb2I7 was determined to be 1.17 eV by UV−vis diffuse-reflectance spectroscopy measurements, Figure 9. Here, optical absorption is dominated by metal−ligand charge transfer transitions within the [AuI4]− unit; thus, it acts as a strong chromophore. This interpretation is supported by the DFT calculations below.

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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10.1021/acs.inorgchem.7b02723

Cite this

@article{69fd7d8a3a43492c95c2760daf081138,

title = "AuPb2I7: A Narrow Bandgap Au3+ Iodide Semiconductor",

abstract = "The unusual Au3+ ternary halide AuPb2I7 has been isolated from reactions of AuI, PbI2, and I2. AuPb2I7 crystallizes in the triclinic P{\=1} space group as micron-scale needles with cell dimensions a = 4.5170(3) {\AA}, b = 7.3847(4) {\AA}, c = 12.2970(7) {\AA}, α = 76.374(4)°, β = 83.711(4)°, γ = 72.987(3)° at room temperature with p = 6.538 g/cm3 and has no structural phase transition down to 100 K. The title compound has a unique three-dimensional structure composed of [Pb2I7]3- pseudolayers extending in [010] bridged by square planar Au3+ at an oblique angle in the [001] direction. The pseudolayers are composed of 1/∞[Pb2I2]2+ chains propagating down [100] linked by square planar I- ions through [010]. AuPb2I7 has a bandgap of 1.17 eV and is stable in air for several days, before degrading to PbI2, Au0, and I2. Density functional theory calculations show that AuPb2I7 is an indirect bandgap semiconductor where the bandgap stems predominantly from Au-I metal-ligand charge transfer.",

author = "Alexander, \{Grant C.B.\} and Fabini, \{Douglas H.\} and Ram Seshadri and Kanatzidis, \{Mercouri G.\}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = jan,

day = "16",

doi = "10.1021/acs.inorgchem.7b02723",

language = "English (US)",

volume = "57",

pages = "804--810",

journal = "Inorganic chemistry",

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AU - Alexander, Grant C.B.

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AU - Seshadri, Ram

AU - Kanatzidis, Mercouri G.

PY - 2018/1/16

Y1 - 2018/1/16

N2 - The unusual Au3+ ternary halide AuPb2I7 has been isolated from reactions of AuI, PbI2, and I2. AuPb2I7 crystallizes in the triclinic P1̄ space group as micron-scale needles with cell dimensions a = 4.5170(3) Å, b = 7.3847(4) Å, c = 12.2970(7) Å, α = 76.374(4)°, β = 83.711(4)°, γ = 72.987(3)° at room temperature with p = 6.538 g/cm3 and has no structural phase transition down to 100 K. The title compound has a unique three-dimensional structure composed of [Pb2I7]3- pseudolayers extending in [010] bridged by square planar Au3+ at an oblique angle in the [001] direction. The pseudolayers are composed of 1/∞[Pb2I2]2+ chains propagating down [100] linked by square planar I- ions through [010]. AuPb2I7 has a bandgap of 1.17 eV and is stable in air for several days, before degrading to PbI2, Au0, and I2. Density functional theory calculations show that AuPb2I7 is an indirect bandgap semiconductor where the bandgap stems predominantly from Au-I metal-ligand charge transfer.

AB - The unusual Au3+ ternary halide AuPb2I7 has been isolated from reactions of AuI, PbI2, and I2. AuPb2I7 crystallizes in the triclinic P1̄ space group as micron-scale needles with cell dimensions a = 4.5170(3) Å, b = 7.3847(4) Å, c = 12.2970(7) Å, α = 76.374(4)°, β = 83.711(4)°, γ = 72.987(3)° at room temperature with p = 6.538 g/cm3 and has no structural phase transition down to 100 K. The title compound has a unique three-dimensional structure composed of [Pb2I7]3- pseudolayers extending in [010] bridged by square planar Au3+ at an oblique angle in the [001] direction. The pseudolayers are composed of 1/∞[Pb2I2]2+ chains propagating down [100] linked by square planar I- ions through [010]. AuPb2I7 has a bandgap of 1.17 eV and is stable in air for several days, before degrading to PbI2, Au0, and I2. Density functional theory calculations show that AuPb2I7 is an indirect bandgap semiconductor where the bandgap stems predominantly from Au-I metal-ligand charge transfer.

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AuPb₂I₇: A Narrow Bandgap Au³⁺ Iodide Semiconductor

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CCDC 1583701: Experimental Crystal Structure Determination

CCDC 1583702: Experimental Crystal Structure Determination

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AuPb2I7: A Narrow Bandgap Au3+ Iodide Semiconductor

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CCDC 1583701: Experimental Crystal Structure Determination

CCDC 1583702: Experimental Crystal Structure Determination

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AuPb₂I₇: A Narrow Bandgap Au³⁺ Iodide Semiconductor