Adrian Portela-Gonzalez, Enrique Mendez-Vega, Wolfram Sander
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2,3,5,6-Tetrafluoro-1,4-phenylenedinitrene: A dinitrene with near degenerate singlet and triplet states
The dinitrene 2,3,5,6-tetrafluoro-1,4-phenylenedinitrene was synthesized by photolysis of matrix-isolated 1,4-diazido-2,3,5,6-tetrafluorobenzene at 365 or 405 nm in high yields at cryogenic temperatures and characterized by FT-IR, UV-Vis, and EPR spectroscopy. The electronic structure of the dinitrene is described best as a quinoidal diradical with an open-shell singlet ground state and a triplet state laying only 650 ± 5 cal/mol higher in energy. Irradiation with λ = 254 nm results in fragmentation of the dinitrene into FCCF and several olefins which on prolonged photolysis fragment into FCCCN, FCCNC, and FCN.
期刊介绍:
The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.