MIKI Sadao Department of Synthetic Chemistry, Kyoto University ; Instructor, 工学部, 助手 (30135537)
KOBAYASHI Tsunetoshi Institute of Physical and Chemical Research., 研究員 (30109798)
MARUYAMA Toshiro Department of Chemical Engineering, Kyoto University ; Instructor, 工学部, 助手 (40026282)
SUGIMOTO Toyonari Department of Synthetic Chemistry, Kyoto University ; Instructor (, 工学部, 助手 (30093256)
TAMARU Yoshinao Department of Synthetic Chemistry, Kyoto University ; Assistant Professor (, 工学部, 助教授 (80026319)
As new electron donors for organic metals, vinylogues of TTF and radialenes possessing 1,3-dithiol-2-ylidene moieties have been synthesized, and electric propeties of their CT-complexes have been studied. Among their CT-complexes with several electon acceptors, the 1 : 1 complex of bis( 1,3-dithiafulvenyl ) with TCNQ revealed high electric aonductivity of <sigma> 300゜K = 16 S/cm. Additionally, the electric conductivity of the complex showed a temperature dependence ressmbling that of metal, indicating that the complex is undoubtedly " organic metal ". The new radialenes, in particular (3)radialene, are expected as desirable electron donors for new types of organic metals, because of their high electron-donating ability and of their high co-planarity.
The electlric properties of (4)radialene-TCNQ ( or TCNQE_4 ) CT complex and of the PF6 and C10_4 salts of (4)radialene cation radical were investigated in compressed pellet or crystal state, and their results suggested the possiblility of o
rganic metals. A possibility preparing the mixed valency state was also suggested.
A number of the donor-acceptor norbornadienes has been prepared, and their efficiencies of storing light energy under solar insolation have been assessed experimentally.
2,3-Dicyano-4,5,6-trimethylnorbornadiene showed the fighest efficiency. The chemical conversion of the norbornadiene to the corresponding quadricyclane under insolation was 5 mol/m^2 day for a typical run which was close to the theoretical one, 6 mol/m^2 day. The development study of the heterogeneous catalyst for the energy-releasing process has been performed begining with a series of fundamental studies including screening of metal elements, reaction mechanisms of metal catalysed cycloreversion, methods for immobilization of catalyst and so forth. Consequently, an excellent heterogeneous catalyst for the cycloreversion of trimethyldicyanoquadricyclane has been found, which revealed many prominent properties, high activity, small deactivation rate and moreover ability of restoration of activity by heating the used catalyst under vacuo. Less