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0345208202
-
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note
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-48 esu is estimated for 1.
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18
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12944260938
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21
-
-
0344777498
-
-
note
-
We also expect d-d transitions to be present in the visible part of the spectrum. However, we expect these to be very weak compared to the two charge-transfer transitions and to make negligible contribution to the observed optical nonlinearity. Therefore, they are not considered further in our discussion.
-
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-
22
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0001082071
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-
24
-
-
0344777496
-
-
note
-
He I and He II PE spectra for p-nitrostyrene, Fc[1]1, Fc[1]2, Rc[1]1, and Oc[1]2 are presented as Supporting Information.
-
-
-
-
27
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37049142388
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Evans, S.; Green, M. L. H.; Jewitt, B.; Orchard, A. F.; Pygall, C. F. J. Chem. Soc., Faraday Trans. 2 1972, 68, 1847-1865.
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28
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-
30
-
-
0345208200
-
-
note
-
Interestingly, the PE spectra of Fc[1]1 and Fc[1]2 are virtually superimposable, except that band B occurs at lower IE in the E-isomer, Fc[1]1. This effect can be attributed to the nonplanar π-system of the Z-isomer leading to a weaker interaction between cyclopentadienyl and p-nitrostyrene π-orbitals; this nonplanarity is evident in the crystal structure reported in ref 4.
-
-
-
-
31
-
-
0344777494
-
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Department of Theoretical Chemistry, Vrije Universiteit, Amsterdam
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Baerends, E. J.; te Velde, G. ADF, version 2.0.1; Department of Theoretical Chemistry, Vrije Universiteit, Amsterdam, 1996.
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0002193879
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Evans, D. H.; O'Connell, K. M.; Peterson, R. A.; Kelly, M. J. J. Chem. Educ. 1983, 60, 290-293.
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-
35
-
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0345208199
-
-
note
-
Low concentrations had to be employed to avoid polymerization on the electrode.
-
-
-
-
37
-
-
0345640162
-
-
note
-
The unusually large g-factor (2.0056 vs 2.00479 in the nitrobenzene radical anion) and the small hyperfine couplings (a = 0.213 G) to the protons in the 2-position of the ferrocen-1-yl unit also indicate some (very limited) delocalization of spin density onto the ferrocene donor.
-
-
-
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38
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0000164888
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Gassman, P. G.; Macomber, D. W.; Hershberger, J. W. Organometallics 1983, 2, 1470-1472.
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33845973581
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33845555055
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-
-
0345640160
-
-
note
-
Interestingly, the difference in ease of oxidation between Fc″[1]2 (-270 mV vs ferrocenium/ferrocene) and the parent octamethylferrocene (-360 mV) is somewhat larger than that between Fc[1]2 (+25 mV) and ferrocene (0 mV). This reflects the greater contribution of charge-transferred resonance structures to the ground state in the stronger donor (octamethylferrocenyl) case.
-
-
-
-
43
-
-
0344345648
-
-
note
-
6).
-
-
-
-
44
-
-
0345640159
-
-
note
-
4 comparison; therefore, it is not surprising that the two bands do not show as similar shifts to one another as in that comparison.
-
-
-
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45
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0001192781
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33947293342
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49
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0344777493
-
-
note
-
xy orbilals (M), which are unaffected by the bridge planarity. These results are also consistent with the UV-PES data for Fc[1]1 and Fc[1]2.
-
-
-
-
50
-
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0000408155
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Kreindlin, A. Z.; Petrovskii, P. V.; Rybinskaya, M. I.; Yanovskii, A. I.; Struchkov, Y. T. J. Organomet. Chem. 1987, 319, 229-237.
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0344777491
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-
note
-
Spectra showing the solvatochromism of Fc″[3]6 are presented in the Supporting Information.
-
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-
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56
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37049085791
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