Structural Modification on Copper(I)-pyridylpyrimidine Complexes for Modulation of Rotational Dynamics, Redox Properties, and Phototriggered Isomerization

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• 作者：Michihiro Nishikawa ; Yusuke Takara ; Yohei Hattori ; Kuniharu Nomoto ; Tetsuro Kusamoto ; Shoko Kume ; Hiroshi Nishihara
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 5, 2013
• 年：2013
• 卷：52
• 期：15
• 页码：8962-8970
• 全文大小：446K
• 年卷期：v.52,no.15(August 5, 2013)
• ISSN：1520-510X

文摘

The redox properties of copper pyridylpyrimidine complexes, which undergo linkage isomerism based on pyrimidine ring rotation, were compared under different coordination environments. A newly synthesized compound, [Cu(Mepypm)(L_Mes)]BF₄ (1路BF₄, Mepypm = 4-methyl-2-(2鈥?pyridyl)pyrimidine, L_Mes = 2,9-dimesityl-1,10-phenanthroline) was compared with previously reported complexes of [Cu(MepmMepy)(L_Mes)]BF₄ (2路BF₄, MepmMepy = 4-methyl-2-(6鈥?methyl-2鈥?pyridyl)pyrimidine), Cu(Mepypm)(DPEphos)]BF₄ (3路BF₄, DPEphos = bis[2-(diphenylphosphino)phenyl]ether), [Cu(Mepypm)(L_Anth)]BF₄ (4路BF₄, L_Anth = 2,9-bis(9-anthryl)-1,10-phenanthroline), and [Cu(Mepypm)(L_Macro)]BF₄ (5路BF₄). Isomer ratios, isomerization dynamics, redox properties, and photoelectron conversion functions varied with the coordination structure. Methyl substituents on the 6-position of the pyridine moiety increased steric repulsion and contributed to quicker rotation, enhanced photoluminescence, and increased photodriven rotational isomerization.