Photo retro-Diels-Alder reactions.

Photo-retro-Diels-Alder (PrDA) reactions of a variety of Diels-Alder (DA) adducts were studied. Experimental results showed that the photoreactivity (quantum yield) depends on the electron-donating ability of the diene component and the electron-withdrawing ability of the dienophile component. The mechanism was studied by trapping the reaction intermediate, O(2) quenching, time-resolved absorption, and fluorescence spectroscopy. All the results support a mechanism that involves a charge-separated intermediate generated from a singlet excited state. The PrDA reaction may find applications in photoresponsive materials, photolithography, drug delivery, and mechanistic research.

[1]  Hiroki Uoyama,et al.  Pentacene precursors for solution-processed OFETs , 2010 .

[2]  Takayoshi Suzuki,et al.  Alternative photoinduced release of HNO or NO from an acyl nitroso compound, depending on environmental polarity. , 2010, Chemical communications.

[3]  Zheng Shi,et al.  Side‐chain free aromatic polyimides containing anthracene units via Diels‐Alder precursors , 2009 .

[4]  Zheng Shi,et al.  Novel organic materials that permanently increase conductivity upon thermal or photo treatment , 2009 .

[5]  Takayoshi Suzuki,et al.  Photoactivatable HNO-releasing compounds using the retro-Diels-Alder reaction. , 2008, Chemical communications.

[6]  Anna K. Croft,et al.  Remote aromatic stabilization in radical reactions , 2008 .

[7]  D. Neckers,et al.  Photodecarbonylation of α-Diketones: A Mechanistic Study of Reactions Leading to Acenes , 2008 .

[8]  M. Kikuchi,et al.  Photochemical synthesis of pentacene and its derivatives. , 2005, Chemistry.

[9]  C. Dimitrakopoulos,et al.  Photosensitive Pentacene Precursor: Synthesis, Photothermal Patterning, and Application in Thin‐Film Transistors , 2003 .

[10]  Jian Yang,et al.  Direct observation of interfacial charge recombination to the excited-triplet state in all-trans-retinoic acid sensitized TiO2 nanoparticles by femtosecond time-resolved difference absorption spectroscopy , 2003 .

[11]  J. Atherton,et al.  Establishing cleavage conditions for an anthracene chiral auxiliary using a photochemical retro Diels-Alder reaction , 2002 .

[12]  Ali Afzali,et al.  High-performance, solution-processed organic thin film transistors from a novel pentacene precursor. , 2002, Journal of the American Chemical Society.

[13]  S. Nutt,et al.  A Thermally Re-mendable Cross-Linked Polymeric Material , 2002, Science.

[14]  T. Tahara,et al.  Vibronic Relaxation of Polyatomic Molecule in Nonpolar Solvent: Femtosecond Anisotropy/Intensity Measurements of the Sn and S1 Fluorescence of Tetracene , 1999 .

[15]  G. Gurzadyan,et al.  Depopulation of Highly Excited Singlet States of DNA Model Compounds: Quantum Yields of 193 and 245 nm Photoproducts of Pyrimidine Monomers and Dinucleoside Monophosphates , 1996, Photochemistry and photobiology.

[16]  R. Grubbs,et al.  Soluble, Highly Conjugated Derivatives of Polyacetylene from the Ring-Opening Metathesis Polymerization of Monosubstituted Cyclooctatetraenes: Synthesis and the Relationship Between Polymer Structure and Physical Properties , 1993 .

[17]  A. W. Czarnik,et al.  Structural effects controlling the rate of the retro-Diels-Alder reaction in anthracene cycloadducts , 1989 .

[18]  Yongseog Chung,et al.  Diene-substituent effects on the rate of the retro-Diels-Alder reaction. Cycloreversion reactivity varying over a range of 105 , 1988 .

[19]  A. W. Czarnik,et al.  Reversal of electronic substituent effects in the retro-Diels-Alder reaction. A charge neutral analog of oxyanion-accelerated cycloreversion , 1986 .

[20]  J. H. Edwards,et al.  New routes to conjugated polymers: 1. A two step route to polyacetylene , 1984 .

[21]  Tadashi. Sasaki,et al.  Molecular design by cycloaddition reactions. XXV. High peri- and regiospecificity of phencyclone , 1976 .

[22]  H. Kwart,et al.  The reverse Diels-Alder or retrodiene reaction , 1968 .

[23]  J. C. Kellett.  A Diels-Alder student preparation , 1963 .

[24]  W. Noland,et al.  The Nef Reaction on 9,10-Dihydro-(11-nitroethano)-anthracenes. A New Route to 9,10-Dihydro-(11-ketoethano)-anthracenes1 , 1956 .

[25]  S. Braslavsky,et al.  Chemical actinometry (IUPAC Technical Report) , 2004 .

[26]  F. Keller,et al.  Bimolecular formation of radicals by hydrogen transfer. 14. The uncatalyzed Transfer Hydrogenation of α‐Methylstyrene by 2,6‐disubstituted 9,10‐Dihydroanthracenes , 1998 .

[27]  Roald Hoffmann,et al.  Stereochemistry of Electrocyclic Reactions (福井謙一とフロンティア軌導理論) -- (参考論文) , 1965 .

[28]  R. Cookson,et al.  The relatives rates of addition of cyano-ethylenes to anthracene and its 9-deuterio- and 9,10-dideuterio-derivatives , 1965 .

[29]  L. Hammett.  The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives , 1937 .