NDLI: Study of nonplanar distortions of Ni(II)-mesomethylporphyrins using spectroscopy of resonance Raman scattering

Content Provider	Springer Nature Link
Author	Terekhov, S. N. Shul'ga, A. M.
Copyright Year	1999
Abstract	The role of mesomethyl substitution and of steric interaction of peripheral substituents in the formation of nonplanar distortions of the porphyrin macrocycle is studied for a series of Ni(II)-porphyrins. Resonance Raman spectra are recorded for Ni(II)-5-methyl-2,3,7,8,12,13,17,18-octaethylporphyrin (1); Ni(II)-2,5,8,12,18-pentamethyl-3,7,13,17-tetraethylporphyrin (2); and Ni(II)-3,5,7,12,17-pentamethyl-2,8,12,17-tetraethylporphyrin (3). The obtained spectra are compared with spectra of Ni-octaethylporphyrin (Ni-OEP) and Ni-etioporphyrin II. It is found that introducing one methyl group into a mesoposition leads to significant low-frequency distortions of the structure-sensitive lines of resonance Raman scattering. Specifically, frequenciesν $_{ 3 }$,ν $_{ 11 }$,ν $_{ 19 }$,ν $_{ 2 }$, andν $_{ 10 }$ decrease by 10–44 cm$^{−1}$ while frequencyν $_{ 4 }$ remains practically unchanged. It is shown that the observed spectral variations are caused by nonplanar distortions of the structure of Ni-porphyrins. The same tendency of the line displacement for tetragonal Ni-OEP and for compounds 1, 2, and 3 indicates that CH$_{3}$-mesosubstituted Ni-porphyrins have a “corrugated” structure. The degree of nonplanarity is modulated by alkyl groups on pyrrole rings and increases in the porphyrin series 3→2→1. All mesomethyl-substituted Ni-porphyrins have spectral indications that the considered compounds are structurally heterogeneous in solution due to the presence of conformers with different degrees of planarity.
Starting Page	180
Ending Page	186
Page Count	7
File Format	PDF
ISSN	00219037
Journal	Journal of Applied Spectroscopy
Volume Number	66
Issue Number	2
e-ISSN	15738647
Language	English
Publisher	Kluwer Academic Publishers-Plenum Publishers
Publisher Date	1999-01-01
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	nonplanarity conformation resonance Raman scattering porphyrins Analytical Chemistry Atomic and Molecular Structure and Spectra
Content Type	Text
Resource Type	Article
Subject	Spectroscopy Condensed Matter Physics

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