Viologen‐based host–guest supramolecule with tunable intramolecular/intermolecular electron transfer chromism and dynamic fluorescence

Abstract

Viologen, as a type of strong electron acceptor, is prone to undergo electron transfer (ET) and change color under external stimuli. However, due to the easy aggregation of viologen molecules, they usually suffer from poor fluorescence emission in the condensed phase. Herein, a new viologen derivative of VioCl2·2Cl (12+·2Cl) was designed and synthesized, in which the fluorescence was enhanced by introducing Me‐β‐CD to weaken the interactions between viologen molecules. Then a viologen‐based host–guest supramolecule of 12+@Me‐β‐CD was obtained by electrostatic interactions. Photo‐/chemo‐responded guest 12+ supplies 12+@Me‐β‐CD, a green and dark purple caused by intramolecular and intermolecular ET. Furthermore, 12+@Me‐β‐CD displays an additional thermal responsive purple color. The triple chromic behaviors all exhibit excellent reversibility and cycling stability. As expected, 12+@Me‐β‐CD exhibits strong photoluminescence (PL) in solid–liquid dual states, presenting an improved quantum yield (Φ) from 12+ (Φs = 0.37%, Φl = 16.74%) to 12+@Me‐β‐CD (Φs = 10.45%, Φl = 25.86%), and the fluorescence intensity can be dynamically modulated by light, heat, and acid/base vapors. The multi‐responsive chromism and tunable fluorescence of 12+@Me‐β‐CD allow for potential applications in information security and smart windows.

Efficient Chromophore Design with PICT Coupled TICT: Computational Studies on Hyperpolarizabilities of Pyridinium Benzimidazolates

“…[4][5][6][7][8][9][10][11][12][13][14][15] Also to be noted here that such kinds of triaryl systems considered here were recently reported to have many useful applications in various areas of material science and are known to show PICT and TICT types of effects. [16][17][18][19] All the molecules considered here have the required D (À vely charged) and A (+ vely charged) sub-fragments, to constitute the push-pull types of zwitterionic systems. As push-pull types of zwitterions are known as suitable materials for optoelectronics, [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] hence in this work detailed quantum mechanical investigations to account for some intrinsic properties, like, dipole moments, quadrupole moments, orbital properties, linear and nonlinear optical properties, etc.…”