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manuscript in preparation
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Evidence for a temperature dependence of solvent mediated coupling in C-shaped DBA molecules has been found. Napper, A.; Read, I.; Zimmt, M.B.; Waldeck, D.H., manuscript in preparation.
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0011111006
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note
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A similar analysis of solvent effects on electron transfer rates in highly curved molecules was previously reported. See ref 6a.
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Charge-transfer distances determined using the Generalized Mulliken Hush Methodol. See ref 12.
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25
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0011077408
-
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note
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This conclusion is supported by prior determinations of |V| for 1 in three of these solvents; ether, acetonitrile and benzonitrile. See ref 3c.
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26
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0011105529
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note
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Molecular solvation models developed by Matyushov incorporate solvent density contributions and reproduce FCWDS variations with temperature accurately. See ref 7, 15.
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30
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0011142317
-
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note
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OX = 0.87 V. All potentials were measured relative to the Ag/AgCl electrode.
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31
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Ph.D. Thesis, Brown University
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1 state of the donor varies between 2.98 and 3.04 eV in these solvents. See Kumar, K. Ph.D. Thesis, Brown University, 1995.
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0011141631
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note
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As noted above, the coupling across the bridge of 1 is presumed to be solvent independent. Thus, only the FCWDS vary with solvent.
-
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41
-
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0011142126
-
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note
-
Including all solvents, the calculated FCWDS ratio is 0.085 ± 0.034.
-
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42
-
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0011082116
-
-
note
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-1 1 from a prior evaluation was used. See ref 3c.
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43
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0011082791
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note
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2CN 6.9, PhCN 5.5, o-dichlorobenzene 8.4.
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44
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0011082792
-
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note
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ref of this magnitude are certainly possible given the presence of electrolyte in the redox measurements.
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45
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0011141632
-
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note
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2 was 4.2-fold larger than that obtained in the present analysis. At this point, it is not possible to determine if the larger disparity arises from errors in the parameters used to determine FCWDS(T) or from a stronger temperature dependence of |V| in this solvent.
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47
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0011135765
-
-
note
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Solvent refractive index may also contribute to Δ as the solvent electronic polarizability also solvates the superexchange state.
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49
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0000638021
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0011115171
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note
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The absence of literature dielectric constant data for 1,3-dithiolane prevents calculation of the FCWDS in this solvent.
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56
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0011106014
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note
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0011077410
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CC in 2 could vary with solvent polarity and influence its electron-transfer kinetics. The extent of this Coulomb driven reduction of the D/A separation, if it occurs in solution, should be largest in solvents with the smallest dielectric constants. The observed variation of |V(2)| is not correlated with dielectric constant.
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