Electron Spin Resonance Study of the Copper (II) and Cobalt (II) Chelates of 2,3;7,8;12,13;17,18-Tetrakis-(9,10-dihydroanthracene-9,10-diyl)porphyrazine

Oliver, Stuart W., Smith, Thomas D., Hanson, Graeme R., Lahey, Neil, Pilbrow, John R. and Sinclair, Geoffrey R. (1987) Electron Spin Resonance Study of the Copper (II) and Cobalt (II) Chelates of 2,3;7,8;12,13;17,18-Tetrakis-(9,10-dihydroanthracene-9,10-diyl)porphyrazine. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 84 5: 1475-1489.


Author Oliver, Stuart W.
Smith, Thomas D.
Hanson, Graeme R.
Lahey, Neil
Pilbrow, John R.
Sinclair, Geoffrey R.
Title Electron Spin Resonance Study of the Copper (II) and Cobalt (II) Chelates of 2,3;7,8;12,13;17,18-Tetrakis-(9,10-dihydroanthracene-9,10-diyl)porphyrazine
Journal name Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases   Check publisher's open access policy
Publication date 1987
Sub-type Article
DOI 10.1039/F19888401475
Volume number 84
Issue number 5
ISSN 0014-7672
Start page 1475
End page 1489
Total pages 15
Place of publication London, England
Publisher The Faraday Society
Language eng
Subject 030606 Structural Chemistry and Spectroscopy
030201 Bioinorganic Chemistry
Formatted abstract The X-band e.s.r. spectra due to the benzene soluble copper(II) (1a) chelate of 2,3; 7,8; 12,13; 17,18-tetrakis-(9,10-dihydroanthracene-9,10-diyl)porphyrazine and the corresponding cobalt(II) chelate (1b) in the absence and presence of axially coordinating heterocyclic bases have been recorded. Spin Hamiltonian parameters have been determined by computer simulation of the various e.s.r. spectra and, in the case of the copper(II) chelate, compared with those obtained from the copper(II) chelates of certain phthalocyanines. The e.s.r. spectral properties of the cobalt(II) chelate (1b) porphyrazine in benzene solution were found to be remarkably dependent on the water hydration which accompanies the chelate in its isolation, requiring drying of the solution by molecular sieves. Axial coordination of the cobalt(II) centre of the chelate by pyridine, tetrahydrofuran or thiophene results in a large shift in the g⊥ region of the spectrum, observed in the absence of axial coordination, to higher fields while causing a dramatic fall in the numerical values of CoA∥ and CoA⊥. The e.s.r. spectra due to frozen benzene solutions of the cobalt chelate (1b) containing various amounts of N-methylimidazole show that axial coordination of the cobalt(II) chelate centre by one heterocyclic base occurs at low concentrations of N-methylimidazole. At higher concentrations, two modes of binding of the N-methylimidazole may be clearly discerned, one characterized by an e.s.r. spectral component typical of low spin cobalt(II) (g∥ < g⊥) and a very unusual spectrum where the g-values are ca. 1.98.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article
Collection: Centre for Advanced Imaging Publications
 
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