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The εD value was determined from the temperature- modulated absorption changes at the monomer (ΔAM) and dimer (ΔAD) band maxima: ΔAM, ε MΔCM, εDMΔC D and ΔAD, εDΔCD, εMDΔCM. in which εM and εDM are molar absorption coefficients of ZnTPnP, and (ZnTPnP.+)2 at monomer band maximum (735 nm, respectively, and εMD is the molar absorption coefficient of ZnTPnP, at the dimer band maximum 980 nm, The εM and εMD values were determined independently at low initial concentrations at 298 K to be 2.7×103M-1cm-1 0,respectively. Based on the material balance, Δ
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2DPO in Figure S2 in the Supporting Information can be simulated by two discrete oxidation waves at 0.68 and 0.77 eV by using Gaussian functions for the oxidation waves.
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2DPO in Figure S2 in the Supporting Information can be simulated by two discrete oxidation waves at 0.68 and 0.77 eV by using Gaussian functions for the oxidation waves.
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.+ exhibits a single line with unresolved hyperfine structure. The observed ESR spectrum was simulated using the hyperfine coupling (hfc) constants estimated from DFT calculation (B3LYP/3-21G basis set) and literature data (dashed line in Figure S5b and c in the Supporting Information); see: J. Fajer. D. C. Borg, A. Forman, D. Dolphin, R. H. Felton, J. Am. Chem. Soc. 1970, 92, 3451.
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If the electron spin of Zn2DPB, is delocalized over the whole π-system, the ESR spectrum of Zn2DPB, can be simulated with the half values of hfc constants and double numbers of atoms in Zn(Et4Me4PhP, The narrower ESR linewidth of Zn2DPB, is well reproduced by the simulated spectrum see the solid line in Figure S5b in the Supporting Information, Thus, the narrowing of the ESR spectrum of Zn2DPB, together with the observation of the NIR absorption results from the spin delocalization due to the charge resonance effect rather than the fast spin exchange: see: J. R. Norris, R. A. Uphaus, H. L. Crespi, J. J. Katz, Proc. Natl. Acad. Sci. USA 1971, 68, 625, and ref, 11
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