Resonance Raman studies and vibrational analysis of Ni(II) porphyrins
A local coordinate scheme has been established for a 37-atom metalloporphyrin skeleton, which takes into account the phasing of adjacent bond stretches within the pyrrole ring and at the methine bridges. A consistent valence force field has been developed for Ni porpine (NiP), Ni tetraphenylporphine (NiTPP), and Ni octaethylporphyrin (NiOEP) by fitting the observed Raman and IR band frequencies and the {sup 15}N, {sup 13}C, and {sup 2}H isotope shifts with the aid of bond length-force constant relationships. NiP and its isotopomers deuterated at meso (d{sub 4}), pyrrole (d{sub 8}), and meso + pyrrole (d{sub 12}) carbon atoms have been studied by RR and IR spectroscopies. NiTPP and its {sup 15}N{sub 4} (pyrrole), {sup 13}C{sub 4} (methine bridge), d{sub 8} (pyrrole), and d{sub 20} (phenyl) isotopomers have been investigated by RR spectroscopy with variable wavelength excitations in both crystalline and solution phases. NiOEP and its {sup 15}N{sub 4} (pyrrole), d{sub 4} (meso), d{sub 16} (methylene group) isotopomers, as well as d{sub 4} + {sup 15}N{sub 4}, and d{sub 4} + {sup 62}Ni double isotopomers have been systematically studied in solution and in three different crystalline forms by RR spectroscopy with variable wavelength excitations. IR spectra for NiOEP and its NiOEP-d{sup 16} isotopomer are reported.
- Research Organization:
- Princeton Univ., NJ (USA)
- OSTI ID:
- 7165307
- Country of Publication:
- United States
- Language:
- English
Similar Records
Consistent porphyrin force field. 2. Nickel octaethylporphyrin skeletal and substituent mode assignments from sup 15 N, meso-d sub 4 , and methylene-d sub 16 Raman and infrared isotope shifts
Resonance Raman, infrared, and normal coordinate analysis of free-base tetraphenylbacteriochlorin: A model for bacteriopheophytins
Related Subjects
59 BASIC BIOLOGICAL SCIENCES
CARBON 13
CARBON ISOTOPES
CARBOXYLIC ACIDS
CHEMICAL ANALYSIS
DEUTERIUM
EVEN-ODD NUCLEI
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPE APPLICATIONS
ISOTOPES
LASER SPECTROSCOPY
LIGHT NUCLEI
METALLOPROTEINS
NITROGEN 15
NITROGEN ISOTOPES
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
PROTEINS
RAMAN SPECTROSCOPY
SPECTROSCOPY
STABLE ISOTOPES
TRACER TECHNIQUES