The photophysics, crystal and electronic structures of some novel benzene-linked bisimidazole compounds

Several novel disubstituted benzene-bridged bisimidazole derivatives (3a–3h) were prepared and characterized. Their optical properties, crystal structures and quantum chemical calculations were also investigated. The UV–vis spectra observed (λAbsmax: 325–348 nm) in acetonitrile showed low optical band gaps (Egopt: 2.89–3.25 eV). All these compounds display strong fluorescence in solution with emission spectra (λEmmax: 389.5–418 nm) (fluorescence quantum yield in the range 0.46–0.95) and significant Stokes shift (3670–5490 cm−1). The single crystal structures of 3h solvates were presented and discussed. The space groups of 3h solvates (3h1: 3h·2H2O and 3h2: 3h·DMSO·2H2O) were C2/c and P21/c, respectively. Quantum chemical calculations using DFT B3LYP/6-31G(d) showed obvious difference in LUMO (−1.273 to −1.715 eV) and HOMO (−4.838 to −5.296 eV) while they were similar in Egcal (3.393–3.599 eV) values of these compounds. These results demonstrate that these novel disubstituted benzene-bridged bisimidazole derivatives are promising electron-transporting electro luminescent materials and blue-light emitting materials for OLED.