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Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene–Phenylenediyne Bridge
30 July 2021
Two redox and magnetically active perchlorotriphenylmethyl (PTM) radical units have been connected as end-capping groups to a bis(phenylene)diyne chain through vinylene linkers. Negative and positive charged species have been generated, and the influence of the bridge on their stabilization is discussed.
Partial reduction of the electron-withdrawing PTM radicals results in a class-II mixed-valence system with the negative charge located on the terminal PTM units, proving the efficiency of the conjugated chain for the electron transport between the two terminal sites. Counterintuitively, the oxidation process does not occur along the electron-rich bridge but on the vinylene units. The PTM radicals play a key role in the stabilization of the cationic species, promoting the generation of quinoidal ring segments.
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Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene–Phenylenediyne Bridge


Paula Mayorga-Burrezo, Francesc BejaranoJoaquín CalboXiaotao ZhaoJ. Alejandro De SousaVega LloverasMartin R. BryceEnrique OrtíJaume VecianaConcepció Rovira, and Núria Crivillers

J. Phys. Chem. Lett. 2021, 12, 26, 6159–6164
DOI: 10.1021/acs.jpclett.1c01565

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