Accessing One-Dimensional Chains of Halogenoindates(III) in Organic-Inorganic Hybrids

Magdalena Owczarek; Minseong Lee; Vivien Zapf; Wanyi Nie; Ryszard Jakubas

doi:10.1021/acs.inorgchem.2c00374

Accessing One-Dimensional Chains of Halogenoindates(III) in Organic-Inorganic Hybrids

Inorg Chem. 2022 Apr 11;61(14):5469-5473. doi: 10.1021/acs.inorgchem.2c00374. Epub 2022 Mar 26.

Authors

Magdalena Owczarek¹, Minseong Lee², Vivien Zapf², Wanyi Nie¹, Ryszard Jakubas³

Affiliations

¹ Materials and Applications Division, Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
² National High Magnetic Field Lab, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
³ Faculty of Chemistry, University of Wroclaw, F. Joliot Curie 14, 50-383 Wroclaw, Poland.

PMID: 35343233
DOI: 10.1021/acs.inorgchem.2c00374

Abstract

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX₄^-, InX₅^2-, InX₆^3-, or In₂X₁₁^5-. Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here we report for the first time In³⁺-based organic-inorganic hybrids, (C₄H₅N₂S)₂InCl₅ and (C₄H₅N₂S)₂InBr₅, with 1D anionic chains of trans-halide-bridged InX₆ octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C₄H₅N₂S⁺). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In³⁺ ions. The materials show a robust band gap predominantly governed by C₄H₅N₂S⁺ cations. Dielectric relaxation processes in (C₄H₅N₂S)₂InBr₅ arise from the cations' dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In³⁺-based hybrids.