Excitation-Wavelength-Dependent Light-Induced Electron Transfer and Twisted Intramolecular Charge Transfer in N,N-Bis(4'-tert-butylbiphenyl-4-yl)aniline Functionalized Borondipyrromethenes.

Abstract

A series of bis(4'-tert-butylbiphenyl-4-yl)aniline (BBA) functionalized borondipyrromethene (BODIPY) dyads, Dyads 1-3, containing the BBA group tethered to BODIPY moiety either directly or through a phenyl or alkynyl phenyl spacers are synthesized, and the light-mediated charge transfer within the chromophores has been systematically investigated. The crystal structure of Dyad-1 showed a tilt of 44.2° between the BODIPY and BBA molecular planes and intermolecular C-H···π interactions with these moieties. Cyclic voltammetric and computational studies showed that the BBA moiety can act as the electron donor (D) and BODIPY as the electron acceptor (A) and the optical absorption studies revealed that an increase in the conjugation of the linker from Dyad-1 to Dyad-2 resulted in bathochromic shifts. Steady-state fluorescence studies involving photoexcitation of the BBA moiety at 326 nm resulted in the decrease in fluorescence intensity of the BBA, indicating the possibility of sequential occurrence of faster photoinduced energy transfer (PEnT) followed by the photoinduced electron transfer (PET) or solely PET within the dyads, and the driving forces of the charge separation were calculated to be exothermic in all of the employed solvents. Parallel time-resolved fluorescence experiments involving the excitation of BBA moiety also supported the occurrence of charge separation in these dyads. Interestingly, excitation of the BODIPY moiety of Dyad-1 and Dyad-2 at 490 nm in solvents of increasing polarity leads to a red-shifted BODIPY emission with weakened intensity. This spectral behavior indicated the occurrence of emission from the locally excited (LE) state in nonpolar solvents, whereas formation of an LE state followed by the rotation of the chromophores at the D-A bond leads to a low energy twisted intramolecular charge transfer state (TICT), resulting in a charge-separated state BBA+•-BODIPY-• in polar solvents. Furthermore, the hydrophobicity studies involving the solutions of dyads in admixtures of polar tetrahydrofuran (THF) and nonpolar hexanes revealed that when the fraction of hexanes in these mixtures is increased, the emission of BODIPY moiety was observed to be blue-shifted and exhibited enhanced intensity supporting the occurrence of TICT in these dyads.