Structural explanation of the spectral features of the nonsymmetrical complex {2,3,7,8,12,13,17,18-octaethyl-5-[(methylimino)methyl]porphyrinato-κ4N21,N22,N23,N24}palladium(II).
The features of porphyrins defining their functionality are related to their conformational flexibility. The degree of nonplanarity of metalloporphyrins depends directly on the number of substituents, their size and their location. The introduction of substituents in the meso positions of β-substituted porphyrins increases the steric interaction and leads to distortions of the porphyrin core. Increasing the distortion of the porphyrin core would augment the bathochromic (red) shift of the electronic absorption spectra. A new nonsymmetrical 2,3,7,8,12,13,17,18-octaethyl-5-[(methylimino)methyl]porphyrin complex of palladium(II), [Pd(C38H47N5)], was synthesized and characterized by NMR, mass spectrometry and X-ray analysis. The features of the electronic absorption spectrum of the synthesized complex are explained by the planarity of the porphyrin core and the π-system of the imino group orthogonal to it.
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky Prospekt, 31, 119071 Moscow, Russian Federation.
Dina R
DR
Erzina
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky Prospekt, 31, 119071 Moscow, Russian Federation.
Ilya A
IA
Zamilatskov
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky Prospekt, 31, 119071 Moscow, Russian Federation.
Nadezhda M
NM
Kurochkina
V. N. Orekhovich Institute of Biomedical Chemistry, RAMS 10 build. 8, Pogodinskaya Street, 119121 Moscow, Russian Federation.
Gelii V
GV
Ponomarev
Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation.
Victor A
VA
Tafeenko
crystal structure; disorder; electronic absorption spectrum; nonsymmetrical metalloporphyrin; spectral features