Preparation of seven-coordinated hypervalent tin(IV)-fused azobenzene and applications for stimuli-responsive π-conjugated polymer films.

ABSTRACT

Heavy atoms can form highly coordinated states, and their optical properties have attracted much attention. Recently, we have demonstrated that a reversible coordination-number shift of hypervalent tin(IV) from five to six can provide predictable hypsochromic shifts in light absorption and emission properties in small molecules and a π-conjugated polymer film. Herein, we show the preparation of seven-coordinated tin and reveal that the binding constant of the seven coordination with ethylenediamine (EDA, K = 2900 M-1) is 200 times higher than that of six coordination with propylamine (PA, K = 14 M-1) owing to the chelate effect. Moreover, reversible vapochromism of the π-conjugated polymer film was observed upon exposure (λabs = 598 nm and λPL = 697 nm) and desorption (λabs = 641 nm and λPL = 702 nm) of EDA vapor. Furthermore, as a unique demonstration, the thermochromic film was prepared by fixing the seven coordination as the initial state using 1,10-phenanthroline. These optical variations are predictable by quantum chemical calculations. Our findings are valuable for the development of designable and controllable stimuli-responsive materials focusing on the inherent properties of the elements.