Wydział Chemii

Magdalena Owczarek

Minseong Lee

Vivien Zapf

Wanyi Nie

Ryszard Jakubas

2022

Inorganic Chemistry

61

5469-5473

10.1021/acs.inorgchem.2c00374

Naukowa

Angielski

Artykuł

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.

Crystals, Oligomers, deformation, Electrical conductivity, cations

http://dx.doi.org/10.1021/acs.inorgchem.2c00374

https://www.acs.org/content/acs/en.html