Recently, CuI‐ and AgI‐based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb‐based halide perovskite absorbers. However, up to date, only AgI‐based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of CuI‐based analogues. Here we show that, owing to the much higher energy level for the Cu 3d10orbitals than for the Ag 4d10orbitals, CuIatoms energetically favor 4‐fold coordination, forming [CuX4] tetrahedra (X=halogen), but not 6‐fold coordination as required for [CuX6] octahedra. In contrast, AgIatoms can have both 6‐ and 4‐fold coordinations. Our density functional theory calculations reveal that the synthesis of CuIhalide double perovskites may instead lead to non‐perovskites containing [CuX4] tetrahedra, as confirmed by our material synthesis efforts.
- Award ID(s):
- 1565923
- PAR ID:
- 10157326
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 48
- Issue:
- 27
- ISSN:
- 1477-9226
- Page Range / eLocation ID:
- 9959 to 9961
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Recently, CuI‐ and AgI‐based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb‐based halide perovskite absorbers. However, up to date, only AgI‐based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of CuI‐based analogues. Here we show that, owing to the much higher energy level for the Cu 3d10orbitals than for the Ag 4d10orbitals, CuIatoms energetically favor 4‐fold coordination, forming [CuX4] tetrahedra (X=halogen), but not 6‐fold coordination as required for [CuX6] octahedra. In contrast, AgIatoms can have both 6‐ and 4‐fold coordinations. Our density functional theory calculations reveal that the synthesis of CuIhalide double perovskites may instead lead to non‐perovskites containing [CuX4] tetrahedra, as confirmed by our material synthesis efforts.
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In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium–boron bonds on a surface of icosahedral boron clusters. M( i ) cations (M = Cu, Ag, and Au) insert into B–Ru bonds of the (BB)–carboryne complex of ruthenium with the formation of four-membered B–M–Ru–B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B–M⋯Ru interactions that are isolobal to B–H⋯Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B–Au and Au–Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo -{C 2 B 10 } clusters, which feature short Cu–B (2.029(2) Å) and Ag–B (2.182(3) Å) bonds and the shortest Au–B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu( i ) and Au( i ) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M–B bonds.more » « less
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We present a series of borane‐tethered cyclic (alkyl)(amino)carbene (cAAC)‐copper complexes, including a borane‐capped Cu(I) hydride. This hydride is unusually hydridic and reacts rapidly with both CO2 and 2,6‐dimethylphenol at room temperature. Its reactivity is distinct from variants without a tethered borane, and the underlying principles governing the enhanced hydricity were evaluated experimentally and theoretically. These stoichiometric results were extended to catalytic CO2 hydrogenation, and the borane‐tethered (intramolecular) system exhibits ~3‐fold enhancement relative to an intermolecular system.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9dt02100k
