title: Resonance Raman studies of beta-substituted porphyrin systems with unusual electronic absorption properties.
abstract: Zn(II) and Cu(II) porphyrins with beta-conjugated barbiturate functional groups have low-energy electronic transitions which are unusual in that there are two strong bands in the Soret region. Resonance excitation of the two bands shows that each has features characteristic of both the porphyrin and barbiturate groups, with some perturbation to these features caused by the interaction of the two chromophores. The resonance Raman (RR) spectrum (lambda(exc)=413.1 nm) of the 412 nm band shows two bands at 1722 and 1743 cm(-1) attributable to C==O stretches in the substituent. Changes in frequency of porphyrin core modes due to the differing metal centres are reproduced by density functional theory calculations. The Q band RR spectra show modes with anomalous polarization which may be attributed to A(2g) modes, however no overtone or combination bands are observed.
authors.affiliation: Department of Chemistry, University of Otago, Union Place, Dunedin, New Zealand.
authors.forename: Penny J
authors.initials: PJ
authors.lastname: Walsh
authors.forename: Keith C
authors.initials: KC
authors.lastname: Gordon
authors.forename: Pawel
authors.initials: P
authors.lastname: Wagner
authors.forename: David L
authors.initials: DL
authors.lastname: Officer
mesh_terms: D000042:Absorption; D001463:Barbiturates / Q000737:chemistry; D001703:Biophysics / Q000379:methods*; D002627:Chemistry, Physical / Q000379:methods; D003300:Copper / Q000737:chemistry; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D016011:Normal Distribution; D011166:Porphyrins / Q000737:chemistry*; D013059:Spectrum Analysis, Raman / Q000295:instrumentation / Q000379:methods*
chemical_list: D001463:Barbiturates; D008665:Metalloporphyrins; D011166:Porphyrins; D003300:Copper