In the first part of this paper, the syntheses, structural characterization, molecular modeling, and electronic spectra for planar and nonplanar perfluoroalkylated porphyrins, (R(f))(4)P's, are reported. These studies demonstrate that the intrinsic substituent effect of the perfluoroalkyl group on the long-wavelength electronic spectrum of porphyrins is substantial, and similar (in magnitude) to that of a phenyl ring. Moreover, it is shown that out-of-plane distortion of (R(f))(4)P's has a negligible impact on their electronic spectra. These data bolster the findings of our earlier work and demonstrate that nonplanarity of (R(f))(4)P's does not result in a red-shift in their optical spectra. In the second part of this paper, time-dependent density functional spectral calculations (B3LYP/6-311G/TD) for porphine, 5,10,15,20-tetrakis(trifluoromethyl)porphyrin, and 5,10,15,20-tetramethylporphyrin in a variety of ruffled conformations are reported. The results of these studies indicate that (1) substantial ruffling of porphyrins has a negligible effect upon their electronic spectra, (2) similarly small effects upon electronic spectra are predicted if electron-withdrawing or electron-releasing groups decorate the porphyrin periphery, (3) for sterically encumbered porphyrins, ruffling can actually result in hypsochromic shifts in various absorption bands, and (4) the bulk of the red-shift commonly thought to be due to nonplanar distortion actually arises from other substituent effects. These results pose serious challenges to previous theoretical and empirical studies that have sought to find a cause-and-effect relationship between nonplanarity and electronic spectra in porphyrins.

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