635-12-1Relevant articles and documents
Studies in the cycloproparene series: Approaches to cyclopropa[b]tetracenes
Halton, Brian
, p. 1123 - 1126 (1999)
Cyclopropa[b]naphthalene-3,6-dione (2) fails to add furan across the enedione olefinic bond in a Diels-Alder cycloaddition even at 14×105 kPa. In contrast, isobenzofuran (4) adds efficiently at ambient temperature and pressure. The epoxytetracenedione (5) that is formed is air-sensitive and decomposes under conditions employed for dehydration. Aromatization of (5) to cyclopropatetracenedione (6) is not observed despite anthracene-l,4-dione (8) being obtained from its analogous tetrahydro precursor (7) under the same conditions. CSIRO 1999.
Quinone-amine reactions, XIII: Syntheses of quinoxalinones and naphthoquinoxalinone for colour comparison with benzoquinoxalinones
Kallmayer,Seyfang
, p. 607 - 614 (1985)
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Singlet Fission in a Flexible Bichromophore with Structural and Dynamic Control
Aster, Alexander,Zinna, Francesco,Rumble, Christopher,Lacour, Jér?me,Vauthey, Eric
supporting information, p. 2361 - 2371 (2021/02/16)
Singlet fission (SF), i.e., the splitting of a high-energy exciton into two lower-energy triplet excitons, has the potential to increase the efficiency for harvesting spectrally broad light. The path from the photopopulated singlet state to free triplets is complicated by competing processes that decrease the overall SF efficiency. A detailed understanding of the whole cascade and the nature of the photoexcited singlet state is still a major challenge. Here, we introduce a pentacene dimer with a flexible crown ether spacer enabling a control of the interchromophore coupling upon solvent-induced self-aggregation as well as cation binding. The systematic change of solvent polarity and viscosity and excitation wavelength, as well as the available conformational phase space, allows us to draw a coherent picture of the whole SF cascade from the femtosecond to microsecond time scales. High coupling leads to ultrafast SF (2 ps), independent of the solvent polarity, and to highly coupled correlated triplet pairs. The absence of a polarity effect indicates that the solvent coordinate does not play a significant role and that SF is driven by intramolecular modes. Low coupling results in much slower SF (μ500 ps), which depends on viscosity, and leads to weakly coupled correlated triplet pairs. These two triplet pairs could be spectrally distinguished and their contribution to the overall SF efficiency, i.e., to the population of free triplets, could be determined. Our results reveal how the overall SF efficiency can be increased by conformational restrictions and control of the structural fluctuation dynamics.
Generation of Endocyclic Vinyl Carbene Complexes via Gold-Catalyzed Oxidative Cyclization of Terminal Diynes: Toward Naphthoquinones and Carbazolequinones
Shu, Chao,Shi, Chong-Yang,Sun, Qing,Zhou, Bo,Li, Tian-You,He, Qiao,Lu, Xin,Liu, Rai-Shung,Ye, Long-Wu
, p. 1019 - 1025 (2019/01/15)
Carbene cascade reactions involving carbene/alkyne metathesis have attracted much attention over the past decades because this chemistry offers great potential to build complicated cyclic molecules. However, the formed vinyl metal carbenoids in these reactions are limited to exocyclic carbenes, and the generation of endocyclic vinyl carbene complexes remains unexplored. Here, we report an unprecedented gold-catalyzed oxidative cyclization of terminal diynes. Importantly, the generation of endocyclic vinyl carbene complexes was involved in this oxidative cyclization, which is distinctively different from previous protocols. This method allows the facile synthesis of various valuable naphthoquinones and carbazolequinones from readily available diynes under exceptionally mild reaction conditions and features a broad substrate scope and wide functional group tolerance. Moreover, theoretical calculations provide further evidence on the divergent selectivity of this cyclization reaction.