Chemistry - A European Journal
Chemistry - A European Journal
5 years ago

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

Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and Nonlinear Optical Properties
Enrique Ortí, Manuel Souto, Imma Ratera, Joaquín Calbo, Jaume Veciana
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. Take it to the bridge: Three conjugated donor-π-acceptor radical systems based on a tetrathiafulvalene (TTF) electron-donor unit connected to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene bridging units of differing lengths were synthesized and characterized. The linear and nonlinear optical properties of these derivatives have been theoretically calculated and compared with their non-radical analogues.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701623

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