Metalla-supramolecular rectangles as electron reservoirs for multielectron reduction and oxidation |
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Authors: | Kaim Wolfgang Schwederski Brigitte Dogan Akbey Fiedler Jan Kuehl Christopher J Stang Peter J |
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Institution: | Institut für Anorganische Chemie, Universit?t Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany. kaim@iac.uni-stuttgart.de |
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Abstract: | The electron-transfer capacity of molecular rectangle ions Pt(II)(4)(PEt(3))(8)(mu-anth(2-))(2)(mu-L)(2)](4+) with anth = anthracene-1,8-diyl and L = 4,4'-bipyridine (bp) or 1,2-bis(4-pyridyl)ethene (bpe) was investigated in acetonitrile and dichloromethane using cyclic voltammetry, EPR, and UV-vis-near-IR spectroelectrochemistry. The compounds can be reversibly reduced, first in a two-electron process and then via two closely separated one-electron steps. Oxidation was also possible at rather low potentials in a reversible two-electron step, followed by an electrochemically irreversible process. The spectroscopic results indicate reduction at the neutral acceptor ligands L and oxidation at the formally dianionic anthracene "clips". In contrast, the prototypical molecular square (Pt(triphos)(mu-bp)](4))(8+) undergoes only irreversible reduction. |
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