Enhancement of Long-Lived Persistent Room-Temperature Phosphorescence and Anion Exchange with I- and SCN- via Metal-Organic Hybrid Formation.

Abstract

An in-depth understanding of structure-property relationships and the construction of multifunctional stimuli-responsive materials are still difficult challenges. Herein, we discovered a 4,4'-bipyridinium derivative with both photochromism and dynamic afterglow at 77 K for the first time. A one-dimensional (1D) Cd(II) coordination polymer (1) assembled by only a 4,4'-bipyridinium derivative and cadmium chloride showed photochromism, room-temperature phosphorescence (RTP), and electrochromism. Interestingly, we found that 1 underwent single-crystal-to-single-crystal transformation during the anion exchange process, and the color of the crystal changed from colorless to yellow (1-SCN-) within 10 min. Complex 1 exhibited photochromism, whereas 1-SCN- did not. The difference in the photochromic behavior between the two complexes was ascribed to the electron transfer pathway between the carboxylate groups and viologen. The DFT calculation based on the crystal structure of 1-SCN- indicated that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were mainly located on bipyridine and cadmium atoms, eliminating the possibility of electron transfer, whereas for complex 1, electron transfer was probable from O and Cl atoms to pyridinium N atoms in viologen as demonstrated by density of states (DOS) calculations. In addition, complex 1 was successfully made into test paper for the rapid detection of I- and SCN- and displayed potential applications in inkless printing, multiple encryption, and anticounterfeiting.