21-Telluraporphyrins. 1. Impact of 21,23-Heteroatom Interactions on Electrochemical Redox Potentials, 125Te NMR Spectra, and Absorption Spectra
2002-06-07T00:00:00Z (GMT) by
meso-Tetraphenyl-21-chalcogenaporphyrins 4−6 (S, Se, and Te as 21-chalcogen atoms, respectively) and meso-tetraphenyl-21,23-dichalcogenaporphyrins 7−10 [(S,S), (Se,S), (Se,Se), and (Te,S) combinations as 21,23-chalcogen atoms, respectively] were prepared by condensation of the appropriate 2,5-bis(phenylhydroxymethyl)chalcogenophene 11 with (1) benzaldehyde, pyrrole, tetrachlorobenzoquinone (TCBQ), and boron trifluoride etherate for the preparation of 4−6 or (2) the appropriate 2,5-bis(1-phenyl-1-pyrrolomethyl)chalcogenophene 13, TCBQ, and boron trifluoride etherate for the preparation of 7−10. Electrochemical oxidation and reduction potentials were measured by cyclic voltammetry for 4−10 and indicated that oxidation of 21-telluraporphyrins 6 and 10 was more facile (more cathodic) than for the other analogues in the series and 10 was more readily oxidized than 6. The band I absorption maxima of 21-telluraporphyrins 6 and 10 were at shorter wavelengths than those of the corresponding analogues containing only sulfur and/or selenium chalcogen atoms. The extinction coefficients, ∈, of the Soret bands of 6 and 10 were 7.6 × 104 and 7.2 × 104 M-1 cm-1, respectively, which is significantly smaller than analogues 4, 5, and 7−9, which have corresponding values of >2 × 105 M-1 cm-1. The 125Te NMR spectrum of 6 gave a chemical shift of δ 834. Oxidation of 6 to oxotelluraporphyrin 12 gave a 125Te NMR chemical shift of δ 1045. 21-Tellura-23-thiaporphyrin 10 gave a 125Te NMR chemical shift of δ 1039, perhaps reflecting deshielding of the Te nucleus by the less than van der Waals contact with the S nucleus.
CC BY-NC 4.0