Semi-empirical AM1 and ZINDO/S,as well as density function theory(DFT)method B3LYP/6-31G(d)quantum chemical calculations were carried out to study the electronic structures and optical properties of poly(p-phenylene vinylene)derivatives(PPVs)with 10 and 11 phenylene rings in the backbone.The calculations suggest that the assembly of alternate incorporation of CN and alkoxy substituted phenylene rings in the PPV backbone could be a good way to construct organic semiconductors with low HOMO/LUMO energy band-gaps.The effect of the end-group on the electronic structures and optical properties of the conjugated polymer was investigated by the calculated UV-Vis and UPS spectra.It was demonstrated that the aldehyde and phosphate end-groups have limited effects on the photophysical properties in the UV-Visible range.
Vinylsilafluorene(VSiF) was successfully synthesized and copolymerized with vinylcarbazole and methyl methacrylate via free radical copolymerization for the first time.The synthesis,photophysical properties,computational modeling studies,and organic light-emitting devices of the VSiF copolymers were presented.The good coordinated photoluminescent(PL) spectra with the absorption of blue light-emitting materials and the high energy band-gap of the VSiF copolymers were observed.Higher triplet band gap(3Eg) to host the blue phosphorescent emitters and better HOMO and LUMO than PVK for electron and hole injection and transportation of the VSiF model compounds were revealed by density functional theory(DFT) calculations.The preliminary device results in applications of these copolymers as host materials for green phosphorescent emitters demonstrate the copolymers of VSiF and vinylcarbazole have comparable device performance of polyvinylcarazole(PVK),suggesting a bright future of VSiF as building blocks for host materials.
