6533b839fe1ef96bd12a6676

RESEARCH PRODUCT

Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene-Phenylenediyne Bridge.

Joaquín CalboJaume VecianaPaula Mayorga BurrezoFrancesc BejaranoNúria CrivillersVega LloverasJ. Alejandro De SousaJ. Alejandro De SousaXiaotao ZhaoConcepció RoviraMartin R. BryceEnrique Ortí

subject

endocrine system010405 organic chemistryRadical anion010402 general chemistry01 natural sciences3. Good health0104 chemical sciencesPolitical scienceOxidationGeneral Materials ScienceStilbene analoguePhysical and Theoretical ChemistryPTM radicalMixed-valence speciesHumanitiesDimerizationOligoyne

description

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.

10.1021/acs.jpclett.1c01565https://pubmed.ncbi.nlm.nih.gov/34184906