title: Photochemistry of dianthrylsilanes: a study of sigma,pi-interaction.
abstract: In this article, we demonstrated by the application of time-resolved spectroscopy, X-ray structural analysis and other spectroscopic techniques that 9-Anthrylsilanes exhibits sigma,pi-interaction between 9-anthryl group and the Si-Si linkage in anthryl-disilanes, ASi(2), ASi(2)A, and ASi(3)A which does not occur in the analogous alkyl derivatives as well as the pyrenylsilane derivatives, in spite of the fact that the 0,0-band of PSi(2) is about 12.8 KJ more energetic than that of ASi(2) (Figure 1). More interestingly, the X-ray structural studies reveal that ASi(3)A exists in a butterfly-like structure in agreement with other spectroscopic analyses that the two anthryl groups do not interact in their excited states, while those in ASi(2)A do. This is in contrast to the analogous pyrenylsilanes; the trisilanes exhibits a stronger excimer interaction than that of disilane.(10b) Our results show that the sigma,pi-interactions in ASi(3)A has imparted rigidity to the tri-silyl linkage. Potential applications of anthrylsilanes in material sciences will be explored.(5) This work provides evidence that sigma,pi-interaction between the 9-anthryl group and disilyl linkage does play an important role in the properties of disilanes. We attribute this enhanced sigma,pi-interaction to the nature of the lowest excited state (S(1) state) of anthracenes, the L(a) transition, which has a much higher oscillator strength than the S(1)L(b)-transition of pyrenes (Figure 1). We define the interaction in anthracene as a sigma,pi(S(1,)L(a)) interaction. This interaction lends a substantial barrier to the Si-Si bond with the excited anthryl nucleus in anthrylsilanes. The scope and potential applications of this phenomenon are discussed.
authors.affiliation: Department of Chemistry, the University of Chicago, Illinois 60637, USA.
authors.forename: Ding-Djung H
authors.initials: DD
authors.lastname: Yang
authors.forename: Nien-Chu C
authors.initials: NC
authors.lastname: Yang
authors.forename: Ian M
authors.initials: IM
authors.lastname: Steele
authors.forename: Hui
authors.initials: H
authors.lastname: Li
authors.forename: Ying-Zhong
authors.initials: YZ
authors.lastname: Ma
authors.forename: Graham R
authors.initials: GR
authors.lastname: Fleming