Synthesis of azo-conjugated metalladithiolenes and their photo- and proton-responsive isomerization reactions |
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Authors: | Nihei Masayuki Kurihara Masato Mizutani Jun Nishihara Hiroshi |
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Institution: | Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan. nihei@tsukuba.ac.jp |
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Abstract: | A versatile synthetic method of azo-conjugated metalladithiolenes was developed, and new complexes with various central metals and substituent groups were synthesized. Molecular structures of the azo-conjugated metalladithiolenes of Ni(II), Pd(II), and Pt(II) with diphenylphosphinoethane as a co-ligand were determined by X-ray crystallography. While the energy of the reversible trans-to-cis photoisomerization is considerably lower than that of azobenzene, the thermal stability of the cis form is much higher than that of the organic azobenzene derivatives showing similar low-energy trans-to-cis photoisomerization. A novel proton response of the azo group occurs, and the combination of photoisomerization and protonation leads to a novel proton-catalyzed cis-to-trans isomerization, the rate of which correlates with the redox potential of the metalladithiolene moiety. The study including other azo-conjugated metalladithiolenes has indicated that the protonation is a common feature for the azo-conjugated metalladithiolenes, but trans-to-cis photoisomerization is strongly dependent on the electronic structure of the trans form or a steric effect in the cis form. |
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