Yutaka Tomona, Mori Ichiro, Kurihara Masato, Tamai Naoto, Nishihara Hiroshi
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Inorg Chem. 2003 Oct 6;42(20):6306-13. doi: 10.1021/ic0260466.
Azobenzene-conjugated mononuclear and dinuclear terpyridyl complexes of Co(II), Co(III), and Fe(II) were synthesized, and their photoisomerization behavior was investigated. Co(II) and Co(III) complexes, [tpyCo(tpy-AB)]X(n) and [(Cotpy)(2)(tpy-AB-tpy)]X(n) (tpy-AB = C(15)N(3)H(10)-C(6)H(4)-N=NC(6)H(5), tpy-AB-tpy = C(15)N(3)H(10)-C(6)H(4)-N=NC(6)H(4)-C(15)N(3)H(10), X = PF(6) or BPh(4)), exhibit trans-to-cis photoisomerization by irradiation at 366 nm, and this behavior is dependent on solvents and counterions. For the Co(II) complexes, BPh(4) salts undergo cis-to-trans isomerization in propylene carbonate by both photoirradiation with visible light (435 nm) and heat, indicating that reversible trans-cis isomerization has occurred. Co(tpy-AB)(2)(2) shows a two-step trans-to-cis isomerization process. The trans-cis isomerization behavior of Co(III) complexes was observed only in the solvents with a low donor number such as 1,2-dichloroethane. Fe(II) complexes, [tpyFe(tpy-AB)]X(n) (X = PF(6) or BPh(4)), exhibit slight trans-to-cis photoisomerization due to the energy transfer from the azobenzene moiety to Fe(tpy)(2) moieties.
合成了钴（II）、钴（III）和铁（II）的偶氮苯共轭单核和双核三联吡啶配合物，并研究了它们的光异构化行为。钴（II）和钴（III）配合物，[tpyCo(tpy-AB)]X(n)和[(Cotpy)₂(tpy-AB-tpy)]X(n)（tpy-AB = C₁₅N₃H₁₀-C₆H₄-N=NC₆H₅，tpy-AB-tpy = C₁₅N₃H₁₀-C₆H₄-N=NC₆H₄-C₁₅N₃H₁₀，X = PF₆或BPh₄），通过366 nm的光照表现出反式到顺式的光异构化，并且这种行为取决于溶剂和抗衡离子。对于钴（II）配合物，BPh₄盐在碳酸亚丙酯中通过可见光（435 nm）光照射和加热都发生顺式到反式异构化，表明发生了可逆的反式-顺式异构化。Co(tpy-AB)₂₂表现出两步反式到顺式异构化过程。钴（III）配合物的反式-顺式异构化行为仅在供体数低的溶剂如1,2-二氯乙烷中观察到。铁（II）配合物，[tpyFe(tpy-AB)]X(n)（X = PF₆或BPh₄），由于偶氮苯部分到Fe(tpy)₂部分的能量转移而表现出轻微的反式到顺式光异构化。
