Cation-induced crown porphyrin dimers of oxovanadium(IV)

Thanabal, V. ; Krishnan, V. (1982) Cation-induced crown porphyrin dimers of oxovanadium(IV) Inorganic Chemistry, 21 (10). pp. 3606-3613. ISSN 0020-1669

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Oxovanadium(1V) porphyrins appended with crown ether (benzo-15-crown-5) at the 5 (mono), the 5 and 10/15 (cis/trans bis), the 5, 10, and 15 (tris), and the 5, 10, 15, and 20 (tetrakis) positions have been synthesized. The cation complexation behavior of these cavity-bearing porphyrins has been studied by using optical aborption and ESR spectral methods. The cations K+, Cs+, NH4+, and Ba2+, which require two crown ether cavities for complexation, induce dimerization of the porphyrins. The cation-induced dimerization constants for a representative tetrasubstituted porphyrin vary as K+ > Ba2+ > Cs+ ~ NH4+, and the relative stabilities of the dimers are dependent on the type of the substitution, tetrakis > tris > cis bis. ESR spectra recorded at a sample temperature of 77 K have low-field components attributed to ΔMh = ± 2 transitions, providing further evidence for the existence of dimers in solutions. The eclipsed sandwich dimers have V-V distances in the range 4.70 Å. The relative distributions of oxovanadium crown porphyrins in terms of monomeric and dimeric forms rest on the geometric dispositions of the crown ether appendages.

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Source:Copyright of this article belongs to American Chemical Society.
ID Code:17315
Deposited On:16 Nov 2010 07:59
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