L. Marcoux, A. Lomax, A. Bard
1970
Citations
0
Influential Citations
16
Citations
Journal
Journal of the American Chemical Society
Abstract
Both the anodic and cathodic electrochemistry of 9,10-di(a-naphthyl)anthracene were studied. It was found to be oxidized in methylene chloride to a cation radical which slowly decompoked to another electroactive species. The reduction proceeded through two one-electron steps, the first reversible, the second irreversible. The esr spectra of both the cation and anion radicals were obtained and interpreted. The angle between the anthracene and naphthalene nuclei was found to be 75’ by both electrochemical and esr techniques. This latter result is discussed in the context of previously determined angles for other molecules. he relief of steric s t ra in b y twisting about essential T single bonds is a chemical phenomenon that has been studied f o r m a n y years i n m a n y ways. The goal of these studies is normally to determine the extent of t h e depar ture f r o m coplanari ty exhibited b y the parts of the molecule in question, and the techniques directed to th is end are most of ten spectroscopic. A frequently cited and studied example is provided b y biphenyl. Aryl-substituted polycyclic a romat ic hydrocarbons have also received a great deal of attention. These latternamed molecules are of special interest because the magnitude of t h e steric repulsion energy is very m u c h a funct ion of the position i n which the aryl substitution occurs. Compare f o r example the different a m o u n t s of steric interaction encountered i n the three isomeric phenylanthracenes. The structures of 9,lO-diphenylanthracene (9,lODPA), 9,10-di(a-naphthyl)anthracene (9,10-DNA), and 9,9’-bianthryl have been discussed on the basis o f their (1) C. Casalone, C. Mariani, A. Mugnoli, and M. Simonetta, Mol. Phys., 15,339 (1968), and references therein. ultraviolet absorpt ion spectra. The ultraviolet spectra of several diand polyphenyl anthracenes have a l so been reported. Molecules such as rubrene and 1,8-diphenylnaphthalene have been the subject o f several studies because of the possible existence of a spiroconjugative interaction. p-6 The advent of sophisticated SCF techniques has made the quant i ta t ive interpretation of electronic spectra possible. Tinland has applied calculations of this type to.naphthy1and phenylsubstituted naphthalenes, anthracenes, and phenant h r e n e ~ . ~ * * A similar approach has also been followed f o r 2-phenylnaphthalene and some of its derivative^.^^'^ (2) R. N. Jones, J . Am. Chem. SOC., 63, 658 (1941). (3) S. D. Dickerman, D. deSouza, and P. Wolf, J . Org. Chem., 30, (4) H. H. Jaffi and 0. Chalvet, J . Am. Chem. SOC., 85, 1561 (1963). (5) H. 0. House, R. W. Magin, and H. W. Thompson, J . Org. Chem., 1981 (1960). 28, 2403 (1963). (6) A. Zweig and J. B. Gallivan, J . Am. Chem. SOC., 91, 260 (1969). (7) B. Tinland, Theoret. Chim. Acta, 11, 385 (1968). (8) B. Tinland. J . Mol. Struct., 2,391 (1968). (9j H. E. Holloway, R. V. Nauman, and J. H. Wharton, J . Phys. Chem., 72,4468 (1968). Marcoux, Lomax, Bard I Electrochemistry and Esr of’9,lODi(a-naphthyl)anthracene