Nondestructive All-Optical Readout through Photoswitching of Intramolecular Excimer Emission

J Phys Chem Lett. 2022 Dec 1;13(47):10936-10942. doi: 10.1021/acs.jpclett.2c02960. Epub 2022 Nov 18.

Abstract

We report the first intramolecular excimer photoswitching induced by molecular motion within a dithienylethene (DTE) molecule without destructive readout. The photochromic compound DTE bears two pyrene chromophores, judiciously positioned to face each other in the DTE's open form. The close proximity of the pyrenes in the open form is confirmed by NMR experiments and geometry optimization. Intense pyrene excimer luminescence is recorded, upon both one- and two-photon excitation (OPE and TPE). The photocyclization reaction of the DTE core induces a molecular motion of one pyrene moiety which thus prevents the possibility of formation of an excimer. Our DTE-based pyrene is stable upon TPE irradiation and shows a high photocyclization quantum yield. Such property specifications allow us to report the original nondestructive readout fluorescence by alternating exposure to OPE and TPE.