Metalla-Supramolecular Rectangles as Electron Reservoirs for Multielectron Reduction and Oxidation
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Abstract
The electron-transfer capacity of molecular rectangle ions [PtII4(PEt3)8(μ-anth2-)2(μ-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)(μ-bp)]4}8+ undergoes only irreversible reduction.
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