ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The radical anions of the compounds N1N, N3N and N5N, in which two naphthalen π-systems are separated by 1, 3 and 5 spirobonded cyclobutane rings, respectively, and tha tof the reference compound N1, containing one naphthalene π-system and one cyclobutane ring, have been studied by ESR and ENDOR spectroscopy under a variety of experimental conditions. The intramolecular electrons spin transfer between the two π-moieties in N3N.⊖ and N5N.⊖ is slow on the hyperfine time-scale, irrespective of the applied conditions. It is also slow in N1N.⊖, except for media of high solvating power. In such media, with a slight reduction of N1N to its radical anion, a paramagnetic species is observed, the hyperfine data for which are consistent with N1N to its radical anion, a paramagnetic species is observed, the hyperfine data of which are consistent with N1N.⊖, undergoing a fast intramolecular electron spin tansfer. The ESR and ENDOR spectra of this species are superimposed on those characteristic of a slow transfer. It is suggested that the fast and slow transfer involve the syn- and anti-conformations, respectively, since the distance, r, between the two naphthalene π-systems of N1N.⊖ is considerably shorter in the former than in the latter (r = 740 vs. 880 Pm for the distance between the centres of the π-systems). Glassy solutions of exhaustively reduced N1N display signals of the dianion triplet state, whereas no such signals are found for N3N and N5N. The zero-field splitting parameter, D, is 4.7 mT, corresponding to r ≈ 480 pm.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19840670210
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