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- W1988795850 abstract "Molecular complexation of meso -tetraalkylporphyrins (with primary alkyl residues) (alkylpor), para -substituted meso -tetraphenylporphyrins ( para = H, CH 3 , Cl, OCH 3 , NO 2 ) (arylpor) and meso -teramesitylporphyrin (H 2 tmp) with PhSnCl 3 (A I ) and (CH 3 ) 2 SnCl 2 (A II ) led to the red shift of the Soret bands. Comparison of the Soret bands of A I (or A II ) 2 arylpor with those of (A I or A II ) 2 alkylpor shows a red shift of ca. 10–20 nm for the formers with respect to the latters. According to the very similar saddled porphyrin core reported for the dications of H 2 tpp and H 2 t(n-Pr)p with CF 3 COOH, it may be concluded that in addition to the Q (0,0) bands the Soret bands may be also affected by the π-donation of meso -aryl substituents to the porphyrin aromatic system. An overlap between one of the e 1g orbital of phenyl groups and the a 1u orbital of porphyrin core is suggested to explain the observed red shifts in the case of π-donor para -substituents. Very similar red shift of the Soret bands of (A I or A II ) 2 H 2 t(4-OMe)pp and (A I or A II ) 2 H 2 t(4-NO 2 )pp with respect to that of (A I or A II ) 2 H 2 t(n-Pr)p, in spite of the π-electron withdrawing effects of para -NO 2 groups, seems to be resulted in by the π-interaction of LUMOs of (4-NO 2 )phenyl substituent with e g orbital of porphyrin core; this interaction would lead to the stabilization of e g orbital and the observed red shift of the Soret band. However, due to the distribution of electron densities of the a 2u orbital on meso -positions, as well as the central nitrogens, the Q (0,0) bands are more strongly affected by the π-donation of meso -aryl groups to the porphyrin core." @default.
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- W1988795850 date "2008-03-01" @default.
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- W1988795850 title "A UV–vis spectroscopic study of 1:2 adduct formation of some free-base meso-tetraaryl- and meso-tetraalkylporphyrins with PhSnCl3 and (CH3)2SnCl2" @default.
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- W1988795850 doi "https://doi.org/10.1016/j.saa.2007.06.003" @default.
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