Towards ferroelectricity-inducing chains of halogenoantimonates(iii) and halogenobismuthates(iii)

Abstract

A discovered abundance of structures with rare and highly-desired anionic chains is examined to identify structural factors leading to the chains' formation.

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

“…(2Sprm) 2 InCl 5 and (2Sprm) 2 InBr 5 are isomorphous with each other and also with the published (2Sprm) 2 BiCl 5 , (2Sprm) 2 BiBr 5 , (2Sprm) 2 SbCl 5 , and (2Sprm) 2 SbBr 5 . Both compounds crystallize in the centrosymmetric P 2 1 / n space group with two formula units per unit cell and similar cell dimensions: a = 5.310(2), b = 14.886(3), c = 10.356(3) Å, β = 103.87(3)° for (2Sprm) 2 InCl 5 and a = 5.789(2), b = 15.115(3), c = 10.342(3) Å, β = 105.83(3)° for (2Sprm) 2 InBr 5 (100 K data collection; Table S1).…”

“…The significance of this finding lies in the fact that, in general, 1D anionic forms determine the properties of materials more profoundly. For instance, 1D chains’ high susceptibility for deformation in many cases leads to the appearance of desirable properties such as piezo- and ferroelectricity or second-harmonic generation. − An assembly of octahedral units into 1D structures strongly depends, however, on an organic cation incorporated into the system, specifically, its size, type (aromatic vs aliphatic), and proton-donating/accepting abilities defining the intermolecular interactions and hence driving the crystal packing. Whereas there are no specific rules for choosing a cation to obtain a target anionic form, some types of cations show a strong propensity to direct the formation of a particular anionic structure.…”

“…Whereas there are no specific rules for choosing a cation to obtain a target anionic form, some types of cations show a strong propensity to direct the formation of a particular anionic structure. Pyrimidine derivatives, for instance, used with halogenoantimonates­(III) and halogenobismuthates­(III) tend to drive the latter toward rare 1D chains of trans -connected octahedra [∠(X bridging –M–X bridging ) ≈ 180°; M = Bi 3+ /Sb 3+ , X = Cl – , Br – ]. , In the effort to expand the family of anionic forms of In 3+ halides, we decided to investigate whether a similar structural architecture can be formed out of halogenoindates­(III).…”

Supramolecular Diiodine-Bromostannate(IV) Complexes: Narrow Bandgap Semiconductors

“…Metal halide complexes, or halometalates, represent the class of coordination compounds which, apart from fundamental interest (in particular, related to structural chemistry), attracts attention due to numerous areas of materials science where they can be applied. Those include design of ferroelectric and ferroelastic materials [1][2][3][4][5], photocatalysis [6][7][8], luminescence [9][10][11][12][13][14][15], photochromism [16,17], etc. However, the most prominent area is photovoltaics.…”

Dichlorine-containing chlorobismuthate(iii) supramolecular hybrid: structure and experimental studies of stability

“…In our recent reports, 20 we assumed that this family can be expanded by involving other elements, especially those demonstrating the structural diversity of halide complexes. Bismuth is one of the base candidates for this rolethere are over 40 structural types of halobismuthates(III) known so far; [21][22][23][24][25][26][27][28][29] moreover, numerous corresponding polybromo- 30 and polyiodo-derivatives, [31][32][33][34] including mixed-halogen complexes, are known. Here we present the first polychlorochlorobismuthate…”