ABSTRACT:Molecular interactions of 1,4-benzenedithiol (BDT) and 1,4-diethynylbenzene (DEB) were studied in hexane or in toluene at 23-25°C by a UV-spectroscopy to elucidate the mechanism for the polyaddition of BDT to DEB. The solution containing both BDT and DEB showed a broad absorption at 280-380nm. The magnitude of the absorbance gradually increased during storage of the solution. Both BDT and DEB may have molecular interactions in solution and also in the solid state to make complexes of the charge-transfer (CT) type. The equilibrium constant (K) and extinction coefficient (e) were tentatively estimated to be about 40 and 8000-15000 at 310nm in hexane or 5:8 and 8000 in toluene, respectively, at 5 s after mixing the component solutions. As a model system, spectroscopic investigation was also made with systems of thiophenol (TP}-phenylacetylene (PA), TP-DEB and BDT-PA in hexane. These systems exhibited a large equilibrium constant and large extinction coefficient as well as BDT and DEB. Consequently, CT interactions seem to control the polyaddition of BDT to DEB in solution and also in solid state.KEY WORDS 1,4-Benzenedithiol / 1,4-Diethynylbenzene / Polyaddition / Model Addition Compounds / UV-Spectroscopy / Charge-Transfer Interaction / Equilibrium Constant (K) / Extinction Coefficient (e) / Continuous-Variation Method/ Ketelaar Method/ When strong electron-donating monomers are mixed with strong electron-accepting ones, regular alternating copolymers may be formed either by spontaneous m1tlat10n or more commonly in the presence of a free radical initiator.in the thin layer crystals perhaps induced by molecular interaction between BDT and DEB.Previously, the authors found a novel polymer of BDT and DEB in solution 1 or in solid state 2 under UV-or y-ray irradiation. In the case of solid state polymerization, thin layer crystals of the 1: 1 mixture of BDT and DEB are mounted on a glass plate by sublimation of a 1 : 1 mixture of BDT and DEB. The thin layer crystals are readily polymerized under UV-irradiation in high yield. 2 Both BDT and DEB are assumed to be arranged alternatingly This report deals with molecular interactions ofBDT and DEB studied by UV-spectroscopy in solution.
EXPERIMENTAL
BDTand DEBBDT and DEB were prepared by the previous method. 1 • 2 BDT was recrystallized from the ethyl acetate solution, and then sublimed at 70°C under reduced pressure prior to use, mp 97-98°C (97-98°C 1 ). DEB was purified by sublimation at 60°C under reduced pressure prior to use, mp 96.5°C (96.5°C 1 ).