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The synthesis, crystal structures, and optical properties of four ternary and six quaternary halides containing the Rh3+ ion are reported here. Rb3RhCl6 adopts a monoclinic structure with isolated [RhCl6]3− octahedra. Rb3Rh2Cl9, Cs3Rh2Cl9, and Cs3Rh2Br9 crystallize in a vacancy ordered variant of the 6H hexagonal perovskite structure, which contains isolated Rh2X93− (X = Cl, Br) dimers of face-sharing octahedra. Cs2AgRhCl6 and Cs2NaRhCl6 adopt the 12R rhombohedral perovskite structure, featuring [M2RhCl12]7− face-sharing octahedral trimers, connected to one another through rhodium-centered octahedra. A4AgRhCl8 and A4AgRhBr8 (A = CH3CH2CH2CH2NH3+, (CH3)2CHCH2CH2NH3)+) crystallize in a cation-ordered variant of the n = 1 Ruddlesden Popper structure, which features layers of corner-connected octahedra with a chessboard ordering of Ag+ and Rh3+ ions separated by double layers of organic cations. The diffuse reflectance spectra of all compositions studied feature peaks in the visible that can be attributed to spin-allowed d-to-d transitions and peaks in the UV that arise from charge transfer transitions. Electronic structure calculations reveal moderate Rh–X–Ag hybridization when rhodium- and silver-centered octahedra share corners, but minimal hybridization when they share faces. Many of the compositions studied have an electronic structure that is effectively zero-dimensional, but Cs2AgRhCl6 is found to possess a two-dimensional electronic structure. The results are instructive for controlling the electronic dimensionality of compositionally complex halide perovskite derivatives.
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Hybrid Organic–Inorganic Halide Derivatives of the 2H Hexagonal Perovskite Structure
Four quaternary hybrid halide perovskites have been synthesized in hydrohalic acid solutions under hydrothermal conditions. The structures of (CH3NH3)2AgRhX6 and (CH3NH3)2NaRhX6, (X = Cl–, Br–) consist of infinite one-dimensional chains of face-sharing metal-halide octahedra. The structure is closely related to the 2H hexagonal perovskite structure, but the space group symmetry is lowered from hexagonal P63/mmc to trigonal P3 ̅m1 by site ordering of the Rh3+ and Ag+/Na+ cations. All compositions demonstrate broad-spectrum visible light absorption with optical transitions arising from rhodium d-to-d transitions and halide-to-rhodium charge transfer transitions. The bromides show a 0.2 eV red shift in the optical transitions compared to the analogous chlorides. Crystal field splitting energies were found to be 2.6 eV and 2.4 eV for the chloride and bromide compositions, respectively. Band structure calculations for all compositions give rather flat valence and conduction bands, suggesting a zero-dimensional electronic structure. The valence bands are made up of crystal orbitals that are almost exclusively Rh 4d–Cl 3p (Br 4p) π* in character, while the conduction bands have Rh 4d–Cl 3p (Br 4p) σ* character.
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- Award ID(s):
- 2003793
- PAR ID:
- 10507468
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Chemistry of Materials
- Volume:
- 34
- Issue:
- 17
- ISSN:
- 0897-4756
- Page Range / eLocation ID:
- 7705 to 7711
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.chemmater.2c00688
