Journal of the American Chemical Society, Vol.115, No.26, 12366-12377, 1993
Synthesis, Vibrational-Spectra, and Normal-Mode Analysis of Nickel(II) 1,5-Dihydroxy-1,5-Dimethyloctaethylbacteriochlorin - A Model for Bacteriochlorophylls
Resonance Raman (RR) and FT-IR spectra are reported for nickel(II) 1,5-dihydroxy-1,5-dimethyloctaethylbacteriochlorin [Ni(HOEBC)] and its meso-d4 isotopomer. All the in-plane skeletal RR-active modes and most IR-active modes are assigned with the aid of a normal mode analysis by using a force field developed for nickel(II) octaethylporphyrin and by scaling the bond stretch force constants to bond lengths revealed in the crystal structure of nickel(II) octaethylbacteriochlorin. The calculated eigenvectors provide insight into the essential vibrational characteristics of metallobacteriochlorins. The RR spectra of Ni(HOEBC) were acquired with a variety of excitation wavelengths, near resonance with the B(x),Q(x), and Q(y) transitions. The enhancement pattern of the observed RR intensities reveals that the B(x)- and near-Q(y)-resonant spectra are dominated by Franck-Condon-active modes while the Q(x)-resonant spectrum is dominated by vibronically active modes. The B(x)-resonant spectrum also shows significant vibronic scattering, via coupling between the B(x)- and B(y)-excited states. Frequencies correlate well among Ni(II) complexes of octaethylporphine (OEP) and hydroporphyrins for modes containing similar local mode contributions, when allowance is made for C(beta)-C(beta) bond order reduction and the effects of symmetry lowering. Assignments are proposed for the existing RR data on bacteriochlorophyll a.
Keywords:RESONANCE RAMAN-SPECTROSCOPY;RHODOBACTER-SPHAEROIDES R-26;BACTERIAL REACTION CENTERS;PHOTOSYNTHETIC REACTION CENTERS;METHYL BACTERIOPHEOPHORBIDE-A;PRIMARY ELECTRON-ACCEPTOR;RHODOPSEUDOMONAS-VIRIDIS;PROTEIN INTERACTIONS;MOLECULAR-STRUCTURE;CHLOROPHYLL-A