This work presents complete vibrational analysis of a chloride complex of Ni(II) 4,12-ditolyl-16,24-diphenyl-3-thiaporphyrin (SDTDPPNi(II)Cl) and its isotopic derivatives ( 61 Ni(II), -d 6 , and -d 10 ). Five-coordinate SDTDPPNi(II)Cl, SDTDPP 61 Ni(II)Cl, (SDTDPP-d 6 )Ni(II)Cl, and (SDTDPP-d 10 )Ni(II)Cl were investigated by Fourier-Transform infrared (FT-IR), resonance Raman (RR), and electronic absorption (UV-vis) methods. Because the methyl groups of tolyl rings at the para-position have negligible influence on geometry and vibrational spectra of SDTDPPNi(II)Cl, they can be treated as point groups. Thus, geometry optimization and vibrational frequencies were calculated for the 4,12,16,24-tetraphenyl-3-thiaporphyrin (STPPNi(II)Cl) model molecule and its isotopically labeled analogs using Gaussian'03. Moreover, charge distributions (General Atomic Polar Tensor -GAPT) and geometrical aromaticity indexes (Bird's I 5 and Harmonic Oscillator Model of Aromaticity -HOMA) were calculated. All theoretical calculations were performed at the B3LYP level with the LANL2DZ basis set. As is shown, the experimental FT-IR and RR spectra for each compound are reproduced well by the corresponding theoretical spectra.
This work presents a complete vibrational analysis of iron [ Fe (II) and Fe (III)] and nickel [ Ni (II)] complexes with 5,10,15,20-tetraphenyl-21-oxaporphyrin [OTPPH] and 5,20-bis(p-tolyl)-10,15-diphenyl-21-oxaporphyrin [ODTDPPH]. In these porphyrins, a furan ring replaces one of the pyrrole rings. The six-coordinate (OTPP) FeIIICl2 and (ODTDPP) FeIIICl2 as well as the five-coordinate (OTPP) FeIICl and (OTPP) NiIICl complexes were investigated using experimental and theoretical methods. The experimental part of this work involved Fourier-transform absorption infrared (FT-IR), resonance Raman (RR), and electron absorption (UV-vis) measurements for all of the investigated complexes. In the theoretical section, optimized geometries and vibrational frequencies for model compounds are provided. The theoretical calculations were performed at the B3LYP level with the LANL2DZ basis set. Good agreement was achieved between the experimental and theoretical vibrational spectra. In addition, charge distributions (GAPT) and geometrical aromaticity indices (Bird's I5 and HOMA) were calculated and discussed.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.