Friday, February 26th, 2016
Brian W. Williams – Breffke, Jens; Williams, Brian W.; and Maroncelli, Mark. “The Photophysics of Three Naphthylmethylene Malononitriles.” Journal of Physical Chemistry B 119, no. 29 (2015) : 9254-9267.
Brian W. Williams, Professor of Chemistry
The,solvent dependence of the photophysical properties of three naphthylmethylene malononitriles, 1-(1-naphthalenylmethylene)-propanedinitrile (I-MENT), 2-(2-naphthalenylmethylene)-propanedinitrile (2-MN), and 2(3,4-dihydro-1-(2H)-phenathrenylidene)-propanedinitile (r2-MN), was studied in order to determine their potential utility as fluidity probes and to make comparisons to the better, studied, benzylidene malononitriles. Density functional calculations Were used to understand the possible conformational states related to, rotation, about the vinyl-aromatic bond (“tau”). Absorption and emission frequencies, extinction coefficients, fluorescence quantum yields, and, fluorescence lifetimes were measured in 11 representative solvents. Both the computational and experimental results indicate that the So -> Si transitions of these molecules have substantial charge-transfer character and produce highly polar excited states. Emission appears to result from relaxed SI states which do not differ qualitatively from the Franck-Condon states reached by absorption. In 2-MN, time resolved emission reveals the presence of two ground-state conformers (“a” and “b” differing by similar to 180 degrees rotation, about tau) coexisting in low-polarity solvents. In contrast, 1-MN appears to exist primarily as a single dominant ground-state conformer. Fluorescence lifetimes vary from ps In 1-MN to similar to 200 ps in 2-MN(a) at room temperature. With the exception of 2-MN(a), the lifetimes vary Systematically with solvent in a manner similar to what is observed in the benzylidene malononitriles. Both solvent polarity and fluidity appear to be important determinants of lifetime. The primary mechanism of fluorescence-decay in naphthylmethylene malononitriles, is likely to be the same as that of the benzylidene malononitriles twisting about the double bond in S-1 which leads to rapid internal conversion via a conical intersection with So.
Breffke, Jens; Williams, Brian W.; and Maroncelli, Mark. “The Photophysics of Three Naphthylmethylene Malononitriles.” Journal of Physical Chemistry B 119, no. 29 (2015) : 9254-9267.