Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Inorg Chem. 2013 Aug 5;52(15):8962-70. doi: 10.1021/ic4011295. Epub 2013 Jul 24.
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·BF4, Mepypm = 4-methyl-2-(2'-pyridyl)pyrimidine, L(Mes) = 2,9-dimesityl-1,10-phenanthroline) was compared with previously reported complexes of [Cu(MepmMepy)(L(Mes))]BF4 (2·BF4, MepmMepy = 4-methyl-2-(6'-methyl-2'-pyridyl)pyrimidine), Cu(Mepypm)(DPEphos)]BF4 (3·BF4, DPEphos = bis[2-(diphenylphosphino)phenyl]ether), [Cu(Mepypm)(L(Anth))]BF4 (4·BF4, L(Anth) = 2,9-bis(9-anthryl)-1,10-phenanthroline), and [Cu(Mepypm)(L(Macro))]BF4 (5·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.
铜的吡啶嘧啶配合物的氧化还原性质，这些配合物基于嘧啶环的旋转发生键异构现象，在不同的配位环境下进行了比较。比较了一种新合成的化合物[Cu（Mepypm）（L（Mes））]BF4（1·BF4，Mepypm=4-甲基-2-（2′-吡啶基）嘧啶，L（Mes）=2,9-二甲基-1,10-菲咯啉）与之前报道的[Cu（MepmMepy）（L（Mes））]BF4（2·BF4，MepmMepy=4-甲基-2-（6′-甲基-2′-吡啶基）嘧啶）、Cu（Mepypm）（DPEphos）]BF4（3·BF4，DPEphos=双[2-（二苯基膦基）苯基]醚）、[Cu（Mepypm）（L（Anth））]BF4（4·BF4，L（Anth）=2,9-双（9-蒽基）-1,10-菲咯啉）和[Cu（Mepypm）（L（Macro））]BF4（5·BF4）的配合物。异构体比例、异构化动力学、氧化还原性质和光电子转换功能随配位结构而变化。吡啶部分 6-位上的甲基取代基增加了空间排斥作用，有助于更快的旋转，增强了光致发光，并增加了光驱动的旋转异构化。
