Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers

Abstract

Adducts of bismuth trihalides BiX 3 (X = Cl, Br, I) and the PS 3 ligand ( PS 3 = P(C 6 H 4 - o -CH 2 SCH 3 ) 3 ) react with HCl to form inorganic/organic hybrids with the general formula [H PS 3 BiX 4 ] 2 . On the basis of their solid-state structures determined by single-crystal X-ray diffraction, these compounds exhibit discrete bis-zwitterionic assemblies consisting of two phosphonium units [H PS 3 ] + linked to a central dibismuthate core [Bi 2 X 8 ] 2– via S→Bi dative interactions. Remarkably, the phosphorus center of the PS 3 ligand undergoes protonation with hydrochloric acid. This is in stark contrast to the protonation of phosphines commonly observed with hydrogen halides resulting in equilibrium. To understand the important factors in this protonation reaction, 31 P NMR experiments and DFT computations have been performed. Furthermore, the dibismuthate linker was utilized to obtain the coordination polymer {[Ag PS 3 BiCl 3 (OTf)] 2 (CH 3 CN) 2 } ∞ , in which dicationic [Ag( PS 3 )] 2 2+ macrocycles containing five-coordinate silver centers connect the dianionic [Bi 2 Cl 6 (OTf) 2 ] 2– dibismuthate fragments. The bonding situation in these dibismuthates has been investigated by single-crystal X-ray diffraction and DFT calculations (NBO analysis, AIM analysis, charge distribution).

Influence of crystal structure and composition on optical and electronic properties of pyridinium-based bismuth iodide complexes

“…1 Corner, edge, or face-sharing of MI 6 octahedral fragments can give rise to zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D) or even three-dimensional (3D) architectures. [2][3][4] The electronic and photoelectronic properties of these structures and their applications are heavily influenced by the counterion. However, concerns over the toxicity of lead halide complexes and the instability of lead(II) halide complexes, have propelled research into environmentally friendly alternatives.…”