Electron Transfer through Norbornadiene and Quadricyclane Moieties as a Model for Molecular Switching
Electron Transfer through Norbornadiene and Quadricyclane Moieties as a Model for Molecular Switching
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通过降冰片二烯和四环烷部分进行电子转移作为分子开关模型
DOI：
10.1021/ic9507225
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发表时间：
1996
影响因子：
4.6
通讯作者：
C. Bignozzi
中科院分区：
文献类型：
--
作者：
P. Lainé;V. Marvaud;A. Gourdon;J. Launay;R. Argazzi;C. Bignozzi
已制备并表征了二氰基降冰片二烯的双（五氨合钌（II））络合物。通过在甲醇中照射，其光化学转化为二氰基四环烷络合物，并通过紫外可见光谱、红外光谱、1H NMR 光谱和循环伏安法进行跟踪。当氧化为钌(II)-钌(III)态时，二氰基降冰片二烯配合物在1000−1600 nm范围内表现出间隔跃迁。这样可以确定通过二氰基降冰片二烯配体的有效耦合 Vab，结果为 0.023 eV。在二氰基四环烷络合物的情况下没有观察到这样的带。这些结果表明通过使用可光致异构化的桥连配体来调节分子内电子转移过程的可能性。
The bis(pentaammineruthenium(II)) complex of dicyanonorbornadiene has been prepared and characterized. Its photochemical conversion into a dicyanoquadricyclane complex by irradiation in methanol has been followed by UV−visible spectroscopy, IR spectroscopy, 1H NMR spectroscopy, and cyclic voltammetry. The dicyanonorbornadiene complex exhibits an intervalence transition in the 1000−1600 nm range when oxidized to the ruthenium(II)−ruthenium(III) state. This allows the determination of the effective coupling Vab through the dicyanonorbornadiene ligand, which is found as 0.023 eV. No such band is observed in the case of the dicyanoquadricyclane complex. These results show the possibility to modulate an intramolecular electron transfer process by using a photoisomerizable bridging ligand.