Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and Nonlinear Optical Properties

Three conjugated donor-π-acceptor radical systems (1 a–1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence of the intramolecular charge transfer on the...

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Detalles Bibliográficos
Autores: Souto Salom, Manuel, Calbo, Joaquín, Ratera, Immaculada, Ortí, Enrique, Veciana, Jaume
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/160784
Acceso en línea:http://hdl.handle.net/10261/160784
Access Level:acceso abierto
Palabra clave:Donor–acceptor complexes
Intramolecular charge transfer
Nonlinear optics
PTM radicals
Tetrathiafulvalene
Descripción
Sumario:Three conjugated donor-π-acceptor radical systems (1 a–1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analyzed by different electrochemical and spectroscopic techniques. Linear optical properties and the second-order nonlinear optical (NLO) response of these derivatives have been computed by comparing systems 1 a–1 c with the non-radical analogues (2 a–2 c). Interestingly, an enhanced NLO response is predicted for dyads 1 a–1 c with PTM in the radical form and for compounds with longer vinylene bridges. Calculations confirm the active role the bridge plays for electronic communication between the donor TTF and the acceptor PTM units.