Photophysical properties of 3-[2-(N-phenylcarbazolyl)benzoxazol-5-yl]alanine derivatives – experimental and theoretical studies

Abstract

Solvatochromic probes are often used in biophysical studies to obtain information about polarity of the microenvironment. As there is not much natural fluorophores with such properties, there is still need for new synthetic compounds such as 3-(2-benzoxazol-5-yl)alanine derivatives. Among this group of non-proteinogenic fluorescent amino acids especially interesting are 3-[2-(4-aminophenyl)benzoxazol-5-yl]alanine derivatives whose solvatochromism depends on the substituents on the nitrogen atom, as revealed by our recent studies. To expand them we synthesized two new derivatives with an N-phenylcarbazole moiety in position 2 of the benzoxazole ring and studied their photophysical properties in solvents of different polarity and ability to form hydrogen bonds using absorption and steady-state and time-resolved fluorescence spectroscopy. Applying single parameter and multi-linear correlations with different solvent parameters, the excited state dipole moments were determined as well as the influence of solvent parameters on each photophysical property was estimated. Moreover, the geometry of compounds and vertical absorption transition were theoretically calculated (DFT and TD DFT methods). It was found that the place of substitution of the N-phenylcarbazole part by the benzoxazole unit determines the character of the electron transition (π–π* or ICT) and thereby the spectral and photophysical properties of the compounds studied.