Structural Modification on Copper(I)-pyridylpyrimidine Complexes for Modulation of Rotational Dynamics, Redox Properties, and Phototriggered Isomerization
Structural Modification on Copper(I)-pyridylpyrimidine Complexes for Modulation of Rotational Dynamics, Redox Properties, and Phototriggered Isomerization
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铜(I)-吡啶基嘧啶配合物的结构修饰，用于调节旋转动力学、氧化还原性质和光触发异构化
DOI：
10.1021/ic4011295
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发表时间：
2013
期刊：
影响因子：
4.6
通讯作者：
and Hiroshi Nishihara
中科院分区：
文献类型：
--
作者：
Michihiro Nishikawa;Yusuke Takara;Yohei Hattori;Kuniharu Nomoto;Tetsuro Kusamoto;Shoko Kume;and Hiroshi Nishihara
比较了在不同配位环境下，发生基于嘧啶环旋转的键合异构化反应的吡啶基嘧啶铜配合物的氧化还原性能。合成了一种新化合物[Cu(Mepypm)(LMES)]BF4(1·BF4，Mepypm=4-甲基-2-(2‘-吡啶)嘧啶，LMES=2，9-二甲基苯基-1，10-菲咯啉)，与已报道的[Cu(MepmMepy)(LMES)]BF4(2·BF4，MepmMepy=4-甲基-2-(6’-甲基-2‘-吡啶)吡啶)，铜(Mepypm)(DPEphos)]BF4(3·BF4，DphPEos=双[2-(二苯基膦)苯基]醚)，[Cu(Mepypm)(Lanth)]BF4(4·BF4，Lanth=2，9-双(9-蒽基)-1，10-菲咯啉)和[Cu(Mepypm)(LMacro)]BF4(5·BF4)。异构化比、异构化动力学、氧化还原性质和光电子转换函数随配位结构的不同而变化。吡啶基团6-位上的甲基取代基增加了空间斥力，加速了旋光，增强了光致发光，增加了光驱动的旋转异构化。
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)(LMes)]BF4(1·BF4, Mepypm = 4-methyl-2-(2′-pyridyl)pyrimidine, LMes= 2,9-dimesityl-1,10-phenanthroline) was compared with previously reported complexes of [Cu(MepmMepy)(LMes)]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)(LAnth)]BF4(4·BF4, LAnth= 2,9-bis(9-anthryl)-1,10-phenanthroline), and [Cu(Mepypm)(LMacro)]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.