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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
Published on: September 26, 2016
Tetrathiafulvalene-Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and
Manuel Souto1, Joaquín Calbo2, Imma Ratera1
1Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de la UAB, 08193, Bellaterra, Spain.
Abstract:
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.
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