Effect of the Addition of a Fused Donor-Acceptor Ligand on a Ru(II) Complex: Synthesis, Characterization, and Photoinduced Electron Transfer Reactions of Ru(TTF-dppz)(2)(Aqphen) (2+)

The synthesis and the photophysical properties of the complex [Ru(TTF-dppz)(2)(Aqphen)](2+) (TTF = tetrathiafulvalene, dppz = dipyrido-[3,2-a:2',3'-c]phenazine, Aqphen = anthraquinone fused to phenanthroline via a pyrazine bridge) are described. In this molecular triad excitation into the metal ligand charge transfer bands results in the creation of a long-lived charge separated state with TTF acting as electron donor and anthraquinone as terminal acceptor. The lifetime of the charge-separated state is 400 ns in dichloromethane at room temperature. A mechanism for the charge separation involving an intermediate charge-separated state is proposed based on transient absorption spectroscopy.

A Donor-Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of Fe(phen)(2)(TTF-dppz)(PF6)(2)

The synthesis and photophysical properties of the complex Fe(phen)(2)(TTF-dppz)(2+) (TTF-dppz = 4',5'-bis-(propylthio)tetrathiafulvenylidipyrido3,2-a:2',3'-c-phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy.

Large π-Conjugated Chromophores Derived from Tetrathiafulvalene

A large π-conjugated chromophore composed of two dipyrido[3,2-a:2′,3′-c]phenazine units directly fused to the central tetrathiafulvalene core has been prepared as a bridging ligand and its strong binding ability to Ru2+ to form a new dinuclear complex is presented. The electronic absorption and luminescence spectra and the electrochemical behavior of the free ligand and the Ru2+ complex have been investigated in detail. The free ligand shows a very strong band in the UV region consistent with ligand-centered π–π* transitions and an intense broad band in the visible region that corresponds to an intramolecular charge-transfer (ILCT) transition. Upon coordination, a metal-to-ligand charge-transfer band appears at 22520 cm−1, and the ILCT band is bathochromically shifted by 1620 cm−1. These electrochemically amphoteric chromophores have also been characterized by spectro-electrochemical 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.