Two novel trimethylsulfonium salts with polymeric {[SbCl₄]⁻}_nor {[CdCl₃]⁻}_nanions

Abstract

The title organic-inorganic hybrid salts poly[trimethylsulfonium [[dichloridoantimony(III)]-di-μ-chlorido]], {(C3H9S)[SbCl4]}n, (I), and catena-poly[trimethylsulfonium [cadmium(II)-tri-μ-chlorido]], {(C3H9S)[CdCl3]}n, (II), consist of trimethylsulfonium cations and polymeric {[SbCl4](-)}n or {[CdCl3](-)}n anions. The central metal atoms are coordinated by six Cl atoms, forming an anionic {[SbCl4](-)}n three-dimensional framework (two of the four bridging chloride anions are located on two different centres of inversion) or anionic {[CdCl3](-)}n one-dimensional chains. The trimethylsulfonium cation of (II) is disordered over two sets of sites in a 0.791 (4):0.209 (4) ratio. All the anions are linked by trimethylsulfonium cations through weak C-H···Cl hydrogen bonds to form three-dimensional structures.

[SMe3]2[Bi2Ag2I10], a silver iodido bismuthate with an unusually small band gap

“…Here, we present a new silver iodido bismuthate, [SMe 3 ] 2 [Bi 2 Ag 2 I 10 ] ( 1 ), that features a one-dimensional ternary anion. We used the trimethyl sulfonium cation [SMe 3 ] + , which has been shown to template halogenido metalates with unusual anion motifs, like [SMe 3 ][SbCl 4 ], the singular example of a halogenido pentelate with a three-dimensional anion structure, 27 and useful properties, like [SMe 3 ][PbI 3 ], an air-stable hexagonal perovskite 28 and [SMe 3 ] 4 [Pb 3 Br 10 ], a layered bromido plumbate with a broad red emission. 29 The anion motif in 1 is deceptively similar to the ones found in [NEt 4 ] 2 [Bi 2 Ag 2 I 10 ] by Chen 23 and [1,3,5-Me 3 py] 2 [Bi 2 Ag 2 I 10 ] by Adonin, 26 however 1 features a band gap of 1.82 eV, much smaller than those found in these previously reported chain-like silver iodido bismuthates.…”

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C2H5NH3)2[BiBr5]

“…Halobismuthates­(III) and haloantimonates­(III) have generated significant interest in the area of inorganic–organic hybrid compounds because of their potential applications as nonlinear dielectric and optical materials. The isoelectronicity of Sb­(III) and Bi­(III) analogues with Sn­(II) and Pb­(II) derivatives, which adopt perovskite structures, stimulates a sharp increase in interest for haloantimonates­(III) and halobismuthates­(III) in the field of optoelectronics. − Recently, special attention has been paid to iodobismuthates­(III) as absorbing Pb-free materials in photovoltaics. − Haloantimonates­(III) and halobismuthates­(III) of the general formula R a M b X 3 b + a (where R = organic cations, M = Sb III or Bi III , and X = Cl, Br, or I) have garnered wide interest because they combine many desirable features, e.g., facile synthesis and processing and cost-effectiveness with promising electrical and optical properties. − These molecular-ionic materials are characterized by a significant diversity of the anionic networks [from zero-dimensional (0D) to one- (1D), two- (2D), or even three-dimensional (3D) architectures]. − With regard to applications, the polar materials are the most promising because the ferroelectricity is limited to only four species, e.g., RMX 4 , , R 3 M 2 X 9 , − R 2 MX 5 , − and R 5 M 2 X 11 . − Tables and contain all known examples of ferroelectrics marked out by the [MX 4 ] − , [M 2 X 9 ] 3– , [MX 5 ] 2– , and [M 2 X 11 ] 5– anions, while Figure illustrates the inorganic structures occurring in ferroelectrics of halobismuthates­(II...…”

Correlation between crystal structures and polar (ferroelectric) properties of hybrids of haloantimonates(iii) and halobismuthates(iii)

“…Haloantimonates (III) and halobismuthates (III) are characterized by a significant diversity of the anionic networks (from zero-, through one-, two-, and three-dimensional architectures). [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Taking into account the molar ratio of the amine (R) and metal (M) (Sb(III)/Bi(III)) the following four basic stoichiometries are observed.…”