The 1,1ʹ-Ethylenebis[4-(methoxycarbonyl)pyridinyl] Diradical and Its Photosensitive Cyclomers

Yusaku Ikegami, Takashi Muramatsu, Kaoru Hanava, Shinji Onodera, Norio Nakayama, Edward M. Kosower

Research output: Contribution to journalArticlepeer-review


One electron reduction of, 1ʹ-ethylenebis[4-(methoxycarbonyl)pyridinium] ion (22+) first gives the cation radical (2), which showed a well-resolved ESR spectrum, and further reduction affords cyclomers formed by intramolecular cyclization of the diradical (2··). Photodissociation of the cyclomers give 2··, which was characterized by an ESR triplet spectrum with the zero field parameters,|D|= 0.0178 and |E| = 0.0017 cm-1, and also by absorption spectrum. Calculations of the D value suggest that the dihedral angle of the N-CH2-CH2-N group of 2·· in a rigid glass is about 75°. Photolysis of the cyclomer via the πσ* state leads to the diradical through rotation around the ring N-CH2bond followed by rotation around the CH2-CH2bond. Assocation of 2··to polydiradical π-complexes at low temperature is proposed on the basis of ESR data and confirmed spectroscopically.

Original languageEnglish
Pages (from-to)2876-2880
Number of pages5
JournalJournal of the American Chemical Society
Issue number10
StatePublished - 1 May 1987


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