Halobismuthate/diphenyliodonium hybrids stabilized by secondary hypervalent I(III)⋯X interactions: Structures, optical studies and thermochromisms.

Diphenyliodonium cations were firstly introduced into halobismuthate system to synthesize two new hybrids, i. e. (DPI) 4 (Bi 2 I 10 ) ( 1 ) and (DPI) 4 (Bi 2 Br 10 )·H 2 O ( 2 ) (DPI = diphenyliodonium). Two hybrids are isostructures containing (Bi 2 X 10 ) 4- halobismuthate dimmers and diphenyliodonium cations. Hypervalent I(III)⋯X interactions and C H⋯X (X I, Br) hydrogen bonds stabilize the structures and contribute to the structural extending from 0-D clusters to 2-D layer/1-D chain. The broader absorption spectra and lower energy gap of 1 were led by strong I⋯I interactions. Two compounds display thermochromism behaviors, whose mechanisms were verified by theoretical calculations. [ABSTRACT FROM AUTHOR]