I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives

Walusiak, Benjamin W.; Raghavan, Adharsh; Cahill, Christopher L.

doi:10.1021/acs.cgd.3c01040

Title: I^–/I₃^– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives

Journal Article · Tue Jan 02 00:00:00 EST 2024 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.3c01040· OSTI ID:2282256

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George Washington University, Washington, DC (United States)

Here, we report a set of three new mixed-valent Au^I Au^III 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 Au^III 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 Au^I···Au^I (aurophilic bonding) and mixed-valent Au^II···Au^IIII 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 Au^I···I interaction type is favored over the Au^III···I.

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Research Organization:: George Washington Univ., Washington, DC (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003996

OSTI ID:: 2282256

Journal Information:: Crystal Growth and Design, Vol. 24, Issue 2; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
perovskite
gold
mixed-valence
crystal
crystallography
iodine
redox
inorganic
anions
crystal structure
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Title: I–/I3– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives

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Title: I^–/I₃^– Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives