科研之友
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摘要
In this paper we present the synthesis as well as a detailed study of the electrochemical and photophysical properties of a series of neutral organic mixed-valence (MV) compounds, 1-7, in which different amine donor centers are connected to perchlorinated triarylmethyl radical units by various spacers. We show that this new class of compounds are excellent model systems for the investigation of electron transfer due to their uncharged character and, consequently, their excellent solubility, particularly in nonpolar solvents. A detailed band shape analysis of the intervalence charge-transfer (IV-CT) bands in the context of Jortner's theory allowed the electron-transfer parameters (inner vibrational reorganization energy lambda(v), outer solvent reorganization energy lambda(o), and the difference in the free energy between the diabatic ground and excited states, Delta G degrees degrees, as well as the averaged molecular vibrational mode (v)) to be extracted independently. In this way we were able to analyze the solvatochromic behavior of the IV-CT bands by evaluating the contribution of each parameter. By comparison of different compounds, we were also able to assign specific molecular moieties to changes in (v). For this class of molecules, we also demonstrate that the adiabatic dipole moment difference Delta mu(ab) and, consequently, the electronic coupling V-12 can be evaluated directly from the absorption spectra by a new variant of the solvatochromic method. Furthermore, an investigation of the electrochemistry of compounds 1-7 by cyclic voltammetry as well as spectroelectrochemistry shows that, not only in the neutral MV compounds but also in their oxidized forms, a charge transfer can be optically induced but with exchanged donor-acceptor functionalities of the redox centers.
- 出版日期2007-5-2
