期刊
DALTON TRANSACTIONS
卷 42, 期 5, 页码 1530-1535出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt31530k
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Three copper(II)@hemicryptophane complexes with various cavity sizes and shapes, Cu(II)@1, Cu(II)@2 and Cu(II)@3, were synthesized and characterized by near-IR/vis and EPR spectroscopies. The spectroscopic data are consistent with the presence of a trigonal-bipyramidal geometry of the N4Cu center dot H2O core, in accord with the energy-minimized structures obtained from DFT calculations. Cyclic voltammetry studies in CH2Cl2 showed irreversible redox processes, whereas electrolysis coulometry indicated that Cu(II)/Cu(I) complexes could be interconverted. Electrochemistry data of the complexes stress the crucial role of the cage structure of the hemicryptophane in the thermodynamics of the electron transfer.
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