Switching of Molecular Insertion in a Cyclic Molecule via Photo- and Thermal Isomerization

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• 作者：Satoshi Umeki ; Shoko Kume ; Hiroshi Nishihara
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：June 6, 2011
• 年：2011
• 卷：50
• 期：11
• 页码：4925-4933
• 全文大小：1130K
• 年卷期：v.50,no.11(June 6, 2011)
• ISSN：1520-510X

文摘

Two new cyclic ligands were synthesized: a ligand with two trans-azobenzene moieties and one bipyridine moiety, trans₂-oAB-O13, and a ligand with two trans-azobenzene moieties and two bipyridine moieties, trans₂-oAB-bpy. Both ligands underwent reversible trans-cis isomerization at the azobenzene moieties. The mole ratios of the trans₂ form:trans-cis form:cis₂ form, evaluated by ¹H NMR spectroscopy of the photostationary states prepared by 1 h illumination, were 0.13:0.27:0.60 (365 nm irradiation) and 0.41:0.47:0.12 (436 nm irradiation) for oAB-O13, and 0.18:0.12:0.70 (365 nm irradiation) and 0.36:0.43:0.21 (436 nm irradiation) for oAB-bpy. When trans₂-oAB-O13 was mixed with Cu(I), both the bipyridine units and the polyether chains coordinated to the copper center. Addition of a noncyclic bipyridine ligand, trans₂-oAB-2OH, afforded a bis(bipyridine)copper(I) complex, [Cu(trans₂-oAB-O13)(trans₂-oAB-2OH)]BF₄. The bis(bipyridine) ligand, trans₂-oAB-bpy, formed a 1:1 complex with Cu(I), [Cu(trans₂-oAB-bpy)]BF₄. [Cu(cis₂-oAB-bpy)]BF₄ did not undergo the ligand substitution reaction with a noncyclic ligand with two azobenzene moieties and one bipyridine moiety, oAB, whereas its thermal isomerization in the presence of oAB caused the formation of [Cu(trans₂-oAB-bpy)(trans₂-oAB)]BF₄, indicating that the isomerization and ligand exchange reactions synchronized via a conformational change of the cyclic ligand.