Solvent-dependent intramolecular charge transfer dual fluorescence of p-dimethylaminobenzanilide bearing steric ortho,ortho-dimethyl substituents at amido aniline

Abstract

Intramolecular charge transfer (ICT) dual fluorescence was observed in various organic solvents with p-dimethylaminobenzanilide (DMBA) derivatives bearing ortho-methyl (DMOMBA) and ortho,ortho-dimethyl (DMDMBA) substituents at amido aniline moiety. Ab initio calculation and absorption spectral data indicated that high steric hindrance was introduced by the ortho,ortho-dimethyl substitutions. It was found that, with DMDMBA, the CT emission initially shifted to the red with increasing solvent polarity from cyclohexane (CHX, 480 nm) to diethyl ether (DEE, 520 nm), similar to those of DMBA derivatives with the ortho-, meta- or para-methyl substitutions at amido aniline moiety. However, there is a characteristic blue-shift of the long wavelength emission between DEE and tetrahydrofuran (THF, 424 nm) then a bathochromic shift again in highly polar solvent acetonitrile (ACN, 484 nm). The unusual solvent-dependent CT emission was ascribed to two competitive CT channels. One is benzanilide (BA)-like CT, whose CT reaction occurs from amido aniline to benzoyl moiety in nonpolar solvent CHX and DEE; the other one is p-dimethylaminobenzamide (DMABA)-like, whose CT reaction occurs from dimethylamino to benzanilide moiety in highly polar solvent THF and ACN. These findings revealed the steric effect plays an important role in the ICT process, which may alter the properties of the electron donor and/or acceptor, but also change the reaction potential.