The effect of conformational isomerism on the optical properties of bis(8-oxyquinolato) diboron complexes with a 2,2′-biphenyl backbone

Abstract

A fluorescent bis(8-oxyquinolato) diborinic complex with a central 2,2′-biphenyl backbone 1 and its octafluoro analogue 2 were synthesized to study the optical–structural relationship of sterically encumbered molecules featuring close intramolecular π-stacking interactions involving chromophore units. The crystal structure of 1 revealed a unique π-stacked arrangement of two pendant phenyl groups and two 8-oxyquinolato ligands (Q) located in the inner part of the complex. Unlike 1, the closely related complex 2 features conformational isomerism, and two major forms, namely 2-syn and 2-anti, are observed in solution to a varying extent depending on the solvent polarity. Form 2-syn, a geometrical analogue of 1, is preferable in polar solutions, whereas its rotational isomer 2-anti featuring π-stacking interactions between the terminal phenyl group and Q ligand dominates in benzene and chloromethane solutions. The observed conformational equilibria strongly affect the optical properties of the system, specifically leading to a significant increase of the quantum yield of emission (from 22% in MeCN to 38% in benzene) accompanied by a bathochromic shift (Δλ = 10 nm) of absorption and hypsochromic shifts (Δλ = −8 nm) of emission spectra with decreasing solvent polarity. This effect was ascribed to the variation in frontier orbital distributions.