title: Four-component fluorescence of trans-1,2-di(1-methyl-2-naphthyl)ethene at 77 K in glassy media. Conformational subtleties revealed.
abstract: The vibronic structure of the fluorescence spectrum of trans-1,2-di(1-methyl-2-naphthyl)ethene (t-1,1) in methylcyclohexane (MCH) solution at room temperature was expected to become better defined upon cooling of the solution to 77 K. Instead, a broad, λexc-dependent fluorescence spectrum was observed in the glassy medium. Vibronically structured t-1,1 fluorescence spectra were obtained in the MCH glass only upon irradiation at the long-λ onset of the absorption spectrum. The application of singular value decomposition with self-modeling on the fluorescence spectral matrices of t-1,1 allowed their resolution into major and minor pairs of vibronically structured spectra that are assigned to two structural modifications of each of two relative orientations of the 1-methyl-2-naphthyl moieties. The difference between the two structures in each pair lies in the direction of rotation of each naphthyl group away from the plane of the olefinic bond. A complex but different conformer distribution is also responsible for the fluorescence spectra of t-1,1 in 5:5:2 (v/v/v) diethyl ether/isopentane/ethyl alcohol (EPA) glass at 77 K. The conformer distributions are also sensitive to the rate of cooling used in glass formation. Conformer distributions based on predicted small energy differences from gas-phase theoretical calculations are of little value when applied to volume-constraining media. The photophysical and photochemical properties of the analogues of the other two conformers of trans-1,2-di(2-naphthyl)ethene, trans-1-(1-methyl-2-naphthyl)-2-(3-methyl-2-naphthyl)ethene (t-1,3) and trans-1,2-di(3-methyl-2-naphthyl)ethene (t-3,3), were determined in solution. However, it is the calculated geometries and energy differences of the t-1,1 conformers [DFT using B3LYP/6-311+G(d,p)] that are essential guides to the interpretation of the experimental results.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306-4390, United States.
authors.forename: Christopher
authors.initials: C
authors.lastname: Redwood
authors.forename: V K Ratheesh
authors.initials: VK
authors.lastname: Kumar
authors.forename: Stuart
authors.initials: S
authors.lastname: Hutchinson
authors.forename: Frank B
authors.initials: FB
authors.lastname: Mallory
authors.forename: Clelia W
authors.initials: CW
authors.lastname: Mallory
authors.forename: Olga
authors.initials: O
authors.lastname: Dmitrenko
authors.forename: Jack
authors.initials: J
authors.lastname: Saltiel