Two Alkyne Derivatives And Their Aggregate Nature

Polydiacetylenes (PDA) system is one of the best third-order nonlinear optical materials in polymers. PDAs exhibit topochemical polymerization and are capable of forming liquid crystals and films as well as single crystal. Polymerization of DAs can be initiated by pressure, heat, UV, orγirradiation (Scheme 1). The PDA, being a one-dimensionalÏ€-conjugated system, shows nonlinear optics (NLO) properties as well as electronic and photonics properties due to conjugated systems. Diacetylenes (DAs) have generated much interest during the last decades due to its peculiar solid state polymerization behavior.For enhancement of the third-order NLO, modification in its substutents is a vital factor. We introduced fluorene groups because of their congugation structures. We also want to adjust arrangement of molecular by introducing alkyl group into fluorene and utilizing Langmuir-Blodgett (LB) technology, so as to reach the requirements for the topochemical solid-state polymerization.1. In this thesis, we prepared two series of diacetylene derivatives. Compounds 2-methyl -4-(9, 9-dibutylfluoren)-3-yn-2-ol (1b), 2-methyl-6-(9, 9-dibutylfluoren)-3, 5-diyn-2-ol (1d), 2-methyl-8-(9, 9-dibutylfluoren)-3, 5, 7-triyn-2-ol (1f), 2-methyl-4-(9, 9-dioctylfluoren)-3-yn-2-ol(2b), 2-methyl-6-(9, 9-dioctylfluoren)-3, 5-diyn-2-ol (2d), 2-methyl-8-(9, 9-dioctyl-fluoren)-3, 5, 7-triyn-2-ol (2f), which have not been reported before (Scheme2). They were characterized by ¹H Nuclear Magnetic Resonance spectra (¹H NMR), ¹³C Nuclear Magnetic Resonance spectra (¹³C NMR), Mass spectra (MS), Infra-red spectra (IR).2. The properties of topochemical solid-stated polymerization of monomers (1d, 1f, 2d, 2f) were investigated by IR and UV when they were initiated by heating at 100℃and deep UV light (250 run) irradiation. According to the results of the IR spectra, these monomers (1d, 1f, 2d, 2f) were polymerized in irregular 1, 2-addtion, 1, 4-addtion, 1, 6-addtion. Fine negative-tone patterns of 1f and 2f were obtained by UV irradiation through a mask, followed development with petroleum ether/ethyl acetate (10:1, v/v) solution. It also indicated that polymerization was happened under the experiment condition. The polymerization behaviors of compound 2f LB films irradiated by deep UV were also investigated.