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I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives
Abstract
Here, we report a set of three new mixed-valent AuI AuIII iodides: (ClPy)3[AuI2]2[AuI4] [1], (BrPy)3[AuI2]2[AuI4] [2], and (ClPy)2[AuI2][AuI4] [3], as well as three new monovalent AuIII iodides: (XPy)2[AuI4][I3] (Py = 4-X-pyridinium X = Cl, Br, and I) [4–6]. Two of these mixed-valent compounds (1 and 2) incorporate both monovalent AuI···AuI (aurophilic bonding) and mixed-valent AuII···AuIIII couples (Au–I halogen bonding), to the best of our knowledge an unprecedented structural feature. These same two mixed-valent compounds also exhibit a rare low-dimensional molecular architecture with respect to second sphere Au···I interactions, namely, 1D chains of Au···I interactions, extending along a single crystallographic axis. All compounds were synthesized with the assistance of the I–/I3– redox couple and tacit manipulation of the polyiodide content during synthesis. Air-free synthesis was used to influence the redox process of I–/I3–, resulting in better selection for mixed-valent products. Compounds 1–2 and 4–5 exhibit a characteristically narrow bandgap (1.04–1.25 eV), as measured via diffuse reflectance spectroscopy (DRS). Computational analyses were used to rationalize the specific assembly modes of [AuI2]– and [AuI4]– species, and they show that the AuI···I interaction type is favored over the AuIII···I.
- Publication Date:
- Research Org.:
- George Washington Univ., Washington, DC (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 2282256
- Grant/Contract Number:
- NA0003996
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Crystal Growth and Design
- Additional Journal Information:
- Journal Volume: 24; Journal Issue: 2; Journal ID: ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; perovskite; gold; mixed-valence; crystal; crystallography; iodine; redox; inorganic; anions; crystal structure; diseases and disorders; materials
Citation Formats
Walusiak, Benjamin W., Raghavan, Adharsh, and Cahill, Christopher L. I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives. United States: N. p., 2024.
Web. doi:10.1021/acs.cgd.3c01040.
Walusiak, Benjamin W., Raghavan, Adharsh, & Cahill, Christopher L. I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives. United States. https://doi.org/10.1021/acs.cgd.3c01040
Walusiak, Benjamin W., Raghavan, Adharsh, and Cahill, Christopher L. Tue .
"I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives". United States. https://doi.org/10.1021/acs.cgd.3c01040.
@article{osti_2282256,
title = {I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives},
author = {Walusiak, Benjamin W. and Raghavan, Adharsh and Cahill, Christopher L.},
abstractNote = {Here, we report a set of three new mixed-valent AuI AuIII iodides: (ClPy)3[AuI2]2[AuI4] [1], (BrPy)3[AuI2]2[AuI4] [2], and (ClPy)2[AuI2][AuI4] [3], as well as three new monovalent AuIII iodides: (XPy)2[AuI4][I3] (Py = 4-X-pyridinium X = Cl, Br, and I) [4–6]. Two of these mixed-valent compounds (1 and 2) incorporate both monovalent AuI···AuI (aurophilic bonding) and mixed-valent AuII···AuIIII couples (Au–I halogen bonding), to the best of our knowledge an unprecedented structural feature. These same two mixed-valent compounds also exhibit a rare low-dimensional molecular architecture with respect to second sphere Au···I interactions, namely, 1D chains of Au···I interactions, extending along a single crystallographic axis. All compounds were synthesized with the assistance of the I–/I3– redox couple and tacit manipulation of the polyiodide content during synthesis. Air-free synthesis was used to influence the redox process of I–/I3–, resulting in better selection for mixed-valent products. Compounds 1–2 and 4–5 exhibit a characteristically narrow bandgap (1.04–1.25 eV), as measured via diffuse reflectance spectroscopy (DRS). Computational analyses were used to rationalize the specific assembly modes of [AuI2]– and [AuI4]– species, and they show that the AuI···I interaction type is favored over the AuIII···I.},
doi = {10.1021/acs.cgd.3c01040},
journal = {Crystal Growth and Design},
number = 2,
volume = 24,
place = {United States},
year = {Tue Jan 02 00:00:00 EST 2024},
month = {Tue Jan 02 00:00:00 EST 2024}
}
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