CONSISTENT PORPHYRIN FORCE-FIELD .2. NICKEL OCTAETHYLPORPHYRIN SKELETAL AND SUBSTITUENT MODE ASSIGNMENTS FROM N-15, MESO-D4, AND METHYLENE-D16 RAMAN AND INFRARED ISOTOPE SHIFTS

Resonance Raman spectra with variable-wavelength excitation are reported for nickel octaethylporphyrin and its isotopomers containing 15N, and 2H at the methine (meso-d4) and methylene (methylene-d16) carbon atoms. The 15N, meso-d4 double isotopomer is also examined. The infrared spectrum of the methylene-d16 isotopomer is reported, and the frequencies are combined with recently published infrared results for the other isotopomers. Essentially all of the porphyrin skeletal modes have been assigned and have been allocated to local coordinates which recognize the pyrrole rings as cooperative vibrational units. The assignments are supported by a normal-coordinate analysis with a valence force field involving standard ethyl force constants and porphyrin in-plane force constants which are transferred nearly intact from Ni porphine and Ni tetraphenylporphyrin. Many vibrational modes of the NiOEP ethyl substituents have also been located in the spectra and assigned. Bands assignable to ethyl C-C stretching and C-H bending modes are surprisingly strong in the resonance Raman spectra and suggest appreciable involvement of the ethyl groups in the porphyrin π-π* excited states. The conformations of the ethyl substituents have a marked influence on the low-frequency vibrational spectra. © 1990 American Chemical Society.