Bismuth-Based Coordination Polymers with Efficient Aggregation-Induced Phosphorescence and Reversible Mechanochromic Luminescence.

Two bismuth coordination polymers (CPs), (TBA)[BiBr4 (bp4mo)] (TBA=tetrabutylammonium) and [BiBr3 (bp4mo)2 ], which are based on the rarely used simple ditopic ligand N-oxide-4,4'-bipyridine (bp4mo), show mechanochromic luminescence (MCL). High solid-state phosphorescence quantum yields of up to 85% were determined for (TBA)[BiBr4 (bp4mo)] (lambdaem =540 nm). Thorough investigations of the luminescence properties combined with DFT and TDDFT calculations revealed that the emission is due to aggregation-induced phosphorescence (AIP). Upon grinding, both samples became amorphous, and their luminescence changed from yellow to orange and red, respectively. Heating or exposure to water vapor led to the recovery of the initial luminescence. These materials are the first examples of mechanochromic phosphors based on bismuth(III).