Thermally Induced Bi(III) Lone Pair Stereoactivity: Ferroelectric Phase Transition and Semiconducting Properties of (MV)BiBr₅ (MV= methylviologen)

Abstract

Regular BiBr5 chains of trans-connected octahedra are stabilized by methyviologen cations. The Bi3+ electron lone pair is sterochemically activated below −30 °C, leading to an acentric polar phase, and this is correlated with an increase of the band gap, and with the transfer from a para- to a ferroelectric phase.

Anionic Metal–Organic Frameworks of Bismuth Benzenedicarboxylates: Synthesis, Structure and Ligand‐Sensitized Photoluminescence

“…The added advantage is that it can exist with or without an active lone pair of electrons, which can be used to fine tune the coordination geometry of the Bi 3+ cation and the collective properties of the materials. [12,13] Compounds containing Bi 3+ cations are also used in oxidation catalysis and can act as lanthanide hosts for optical applications. [14][15][16] Only a few frameworks based on bismuth carboxylates have been reported to date, [17][18][19][20] so we have recently begun to explore the structures and properties of these interesting materials.…”

Structural characterization, thermal, dielectric and vibrational properties of tris(allylammonium) hexabromoantimonate(III), (C3H5NH3)3SbBr6

“…Halogenoantimonates(III) and halogenobismuthates(III) of the general formula R a M b X 3b+a (where R denotes the organic cation, M-Sb(III) or Bi(III) and X-halogen atom: Cl, Br, I) cause much interest because of their unique properties and potential applications as a nonlinear polar and nonlinear optical materials [1][2][3]. Numerous structural studies show that these metal(III) halide complexes are characterized by a rich diversity of the anionic forms [4,5].…”

Synthesis, crystal structure and dielectric properties of C6H18N2SbCl5

“…7(a, b) and À Z″ = f(ω) Figs. 8(a, b) at various temperatures are fitted by means of Eqns (1) and (2). A good agreement between the calculated lines and the experimental data justifies the choice of the equivalent circuit.…”

“…A strong motivation is devoted on the research of this novel class of material because of their interesting applications, such as solid-state batteries, ionic conductors, sensors, photovoltaic cells, etc. [1,2] In the particular case of alkylammonium antimonate (III) chlorides, the following anions can be obtained [SbCl 4 ] À , [3] [SbCl 5 ] 3À [4] and [Sb 2 Cl 11 ] 5À . [5] In these compounds the antimonate Sb(III) cation shows a tendency toward distorted octahedral coordination with some rather long Sb-Cl bonds, which is attributed to the aspherical distribution of the lone pair electrons at Sb(III).…”