Synthesis and photostability of 1,4-bis(5-phenyloxazol-2-yl)benzene (POPOP) structural isomers and their trimethylsilyl derivatives

Abstract

In this work, a versatile synthetic method for preparation of linear phenyloxazoles and their organosilicon derivatives under mild conditions via a combination of van Leusen and direct CH arylation reactions is reported. It was used for the synthesis of a novel trimethylsilyl (TMS) derivative of blue laser dye 1,4-bis(5-phenyloxazol-2-yl)benzene (POPOP) and its structural isomer 1,4-bis(2-phenyloxazol-5-yl)benzene (isoPOPOP) with and without TMS substituents. All of the compounds demonstrated high photoluminescence quantum yields and large molar extinction coefficients, which further increased for their TMS derivatives. Measurements of accelerated photodegradation of the dyes in diluted THF solutions revealed that POPOP-type compounds are twice more stable than their isoPOPOP-type isomers, independent of the presence or absence of TMS substituents. Cyclic voltammetry (CV) investigations revealed that POPOP-type dyes are more electrochemically stable as compared to their isoPOPOP-type isomers. Quantum chemical TD DFT calculations of the frontier energy levels of the dyes were in a good agreement with the experimental data obtained by CV. Single-crystal X-ray diffraction experiments revealed significant structural differences between crystal lattices of the dyes. Due to facile synthesis and excellent optical properties as well as high photo- and thermo- stability the novel luminescent dyes may find wide application in organic photonics.