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.
LIU ShuJuanYANG ChengJiangXU WenJuanHUANG YanQinYE ShangHuiZHAO QiangLIU XiangMeiHUANG Wei
In this work, a near-infrared (NIR) phosphorescent probe for F- based on a cationic Ir(Ⅲ) complex [Ir(Bpq)2(quqo)]PF6 (1) with dimesitylboryl (Mes2B) groups on the cyclometalated C^N ligands (Bpq) and 2-(quinolin-2-yl)quinoxaline (quqo) as N^N ligand was designed and synthesized. The excited state properties of 1 were investigated in detail using molecular orbital cal- culations and experimental methods. Upon excitation, complex 1 shows NIR phosphorescent emission around 680 nm. Inter- estingly, the complex can be excited with long wavelength around 610 nm. Such long-wavelength excitation can reduce the background emission interference and improve the signal-to-noise ratio. Furthermore, the selective binding between boron at- om and F- can give rise to the quenching of emission and realize the near-infrared phosphorescent sensing for F-. We wish that the results reported herein will be helpful for the further design of excellent near-infrared phosphorescent probes based on heavy-metal complexes.
