Oligothienylenevinylene Polarons and Bipolarons Confined between Electron‐Accepting Perchlorotriphenylmethyl Radicals

A detailed analysis is undertaken of positively charged species generated on a series of thienylenevinylene (nTV) wires terminally substituted with two perchlorotriphenylmethyl (.PTM) radical acceptor groups, .PTM‐nTV‐PTM. (n=2–7). Motivated by the counterintuitive key role played by holes in the nTV bridges on the operating mechanism of electron transfer in their radical anion mixed‐valence derivatives, a wide combination of experimental and theoretical techniques is used, with the aim of gaining further insights into their structural location. Consequently, contributions of the .PTM units for the stabilization of the radical cations and hole localization, particularly in the case of the shortest molecular wire, are probed. In this sense, the formation of quinoidal ring segments, resulting from the coupling of the unpaired electron of the .PTM radical site with those generated along the nTV chains is found. Additionally, open‐shell dications, described by the recovery of the central aromaticity and two terminal quinoidal segments, assisted by the .PTM units, are detected.The authors acknowledge the financial support through pro-jects: BE-WELL (CTQ2013-40480-R), FANCY (CTQ2016-80030-R), CTQ2015- 69391-P and CTQ2016-79189-R, grant-ed by the DGI (Spain), GenCat (2014-SGR-17) financed by DGR (Catalunya) and the Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Programme for Centres of Excellence in R&D (SEV-2015-0496) and project PEII-2014-014-P granted by the Junta de Comunidades de Castilla-La Mancha, Spain. This study has been also supported by the Networking Research Center on Bioengineering, Bio-materials and Nanomedicine (CIBER-BBN), an initiative funded by the VI National R&D&I Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and fi-nanced by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. The authors also thank the Research Central Services (SCAI) of the Uni-versity of Málaga. P. M. B. gratefully acknowledges financial support from the Juan de la Cierva-Formación 2015 pro-gramme supported by MINECO. We also acknowledge Dr. Vega Lloveras for the EPR measurements.Peer reviewe