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Title

Large π-Conjugated Chromophores Derived from Tetrathiafulvalene

Authors
Jia, Hongpeng
Decurtins, Silvio
Liu, Shi-Xia
Published in Asian Journal of Organic Chemistry. 2014, vol. 3, no. 2, p. 198-202
Abstract A large pi-conjugated chromophore composed of two dipyrido[3,2-a:2’,3’-c]phenazine (dppz) units directly fused to the central tetrathiafulvalene (TTF) core, has been prepared as a bridging ligand, and its strong binding ability to Ru2+ forming a new dinuclear complex is presented. The electronic absorption and luminescence and the electrochemical behaviour of the free ligand as well as the Ru2+ complex have been investigated in detail. The free ligand shows a very strong band in the UV region consistent with ligand centred π-π* transitions and an intense broad band in the visible region corresponding to an intramolecular charge transfer (ILCT) transition. Upon coordination, a metal-to-ligand charge transfer (MLCT) appears at 22520 cm-1 while the ILCT band is bathochromically shifted by 1620 cm-1. These electrochemically amphoteric chromophores have also been characterized by spectroelectrochemical methods. The oxidized radical species of the free ligand show a strong tendency to undergo aggregation, in which long-distance attractive interactions overcome the electrostatic repulsion. Moreover, these two new chromophores reveal an ILCT fluorescence with large solvent-dependent Stokes shifts and quantum efficiencies of 0.052 for the free ligand and 0.016 for its dinuclear Ru2+ complex in CH2Cl2.
Keywords Dipyrido[3,2-a:2′,3′-c]phenazinesPhotophysicsRedox chemistryRutheniumTetrathiafulvalenes
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Other version: http://doi.wiley.com/10.1002/ajoc.201300144
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Research group Groupe Hauser
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JIA, Hongpeng et al. Large π-Conjugated Chromophores Derived from Tetrathiafulvalene. In: Asian Journal of Organic Chemistry, 2014, vol. 3, n° 2, p. 198-202. https://archive-ouverte.unige.ch/unige:34423

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Deposited on : 2014-02-25

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