The design and development of organic luminophores that exhibit efficient ultraviolet (UV) fluorescence in the solid state remains underexplored. Here, we report that 1,4-dialkenyl-2,5-dialkoxybenzenes and 1,4-dialkenyl-2,5-disiloxybenzenes act as such UV-emissive fluorophores. The dialkenyldioxybenzenes were readily prepared in three steps from 2,5-dimethoxy-1,4-diacetylbenzene or 2,5-dimethoxy-1,4-diformylbenzene via two to four steps from 1,4-bis(diethoxyphosphonylmethyl)-2,5-dimethoxybenzene. The dialkenyldioxybenzenes emit UV light in solution (λem =350-387 nm) and in the solid state (λem =328-388 nm). In addition, the quantum yields in the solid state were generally higher than those in solution. In particular, the adamantylidene-substituted benzenes fluoresced in the UV region with high quantum yields (Φ=0.37-0.55) in the solid state. Thin films of poly(methyl methacrylate) doped with the adamantylidene-substituted benzenes also exhibited UV emission with good efficiency (Φ=0.27-0.45). Density functional theory calculations revealed that the optical excitation of the dialkenyldimethoxybenzenes involves intramolecular charge-transfer from the ether oxygen atoms to the twisted alkenyl-benzene-alkenyl moiety, whereas the dialkenylbis(triphenylsiloxy)benzenes were optically excited through intramolecular charge-transfer from the oxygen atoms and twisted π-system to the phenyl-Si moieties of each triphenylsilyl group.
Keywords: charge transfer; donor-acceptor systems; fluorescence; materials science; photochemistry.
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