Portal de Periódicos da CAPES

Specific coupling between the 13-keto carbonyl and chlorin skeletal vibrational modes of synthetic 131-18O-(un)labelled metallochlorophyll derivatives

2008; Elsevier BV; Volume: 72; Issue: 2 Linguagem: Inglês

10.1016/j.saa.2008.09.016

1873-3557

Hidetada Morishita, Hitoshi Tamiaki,

Porphyrin and Phthalocyanine Chemistry

Metal complexes of methyl 13(1)-(18)O-labelled pyropheophorbide-a1-M-(18)O (M=Zn, Cu and Ni) were prepared by metallation of the (18)O-labelled free base (1-(18)O) and (18)O-labelling of unlabelled nickel complex (1-Ni). The FT-IR spectra of 1-Zn and 1-Zn-(18)O in CH(2)Cl(2) showed that the 13-keto carbonyl stretching vibration mode moved to about a 30-cm(-1) lower wavenumber by (18)O-labelling of the 13(1)-oxo moiety. In 1-Cu-(18)O and 1-Ni-(18)O, the 13-C==(18)O stretching modes were close to the highest-energy wavenumber mode of chlorin skeletal C-C/C-N vibrations at around 1650cm(-1) and they were coupled in CH(2)Cl(2) to give two split IR bands (Fermi resonance). A similar coupling was observed in the resonance Raman scattering of 1-Ni-(18)O in the solid state. The hydrogen-bonded 13-C==(16)O vibration mode of 1-Ni similarly coupled with the skeletal C-C/C-N mode in CCl(4) containing 1% (v/v) 1,1,1,3,3,3-hexafluoro-2-propanol, while such a coupling was not observed in a neat CCl(4) solution of 1-Ni possessing the 13-C==(16)O free from any interaction. The skeletal C-C/C-N band selectively coupled with the 13-C==O, not with the 3-C==O, when the difference in their peak maxima was less than 20 cm(-1).