Effect of metal centres and substituents on the structure and optoelectronic properties of diarylethene compounds: A theoretical study

Diarylethene derivatives are a class of fascinating photochromic materials because of their open and closed isomers with different absorption spectra and many other characteristics. To reveal the detailed structure and optoelectronic properties as well as the effect of metal centres and substituents on them, a systematic study on a series of diarylethene derivatives and their Re(I), Pt(II), and Ir(III) complexes was performed via theoretical calculation. The optimized geometries, electronic properties, frontier molecular orbitals, ionization potentials, electron affinities, reorganization energies, and absorption spectra for both of their open- and closed-isomers have been calculated and analyzed. Metal-coordination and substituents exhibit great influence on the photophysical, charge-injection and -transporting characteristics. In addition, the binding of F^- with the boron atom of dimesitylboryl group through Lewis acid/base interactions also induces great changes of structural, photophysical and electronic properties for these diarylethene derivatives, and consequently the compound with the substituent of dimesitylboryl group can be used as selective near-infrared phosphorescent F^- probe.