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首页> 外文学位 >MECHANISTIC STUDIES OF THE PHOTOCHEMISTRY OF BIPHENYL CONTAINING BICHROMOPHORIC MOLECULES AND THE SYNTHESIS OF MOLECULAR RODS COMPOSED OF BICYCLO(2.2.2)OCTANE UNITS BONDED IN A BRIDGEHEAD TO BRIDGEHEAD MANNER (1,3-CYCLOHEXADIENE).
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MECHANISTIC STUDIES OF THE PHOTOCHEMISTRY OF BIPHENYL CONTAINING BICHROMOPHORIC MOLECULES AND THE SYNTHESIS OF MOLECULAR RODS COMPOSED OF BICYCLO(2.2.2)OCTANE UNITS BONDED IN A BRIDGEHEAD TO BRIDGEHEAD MANNER (1,3-CYCLOHEXADIENE).

机译：含联苯的双酚分子的光化学机理和双桥（2.2.2）OCEANE单元在桥头与桥头方式（1,3-环己二烯）键合中分子杆的合成。

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摘要

The photochemistry of 4,4-dibiphenylylcyclohex-2-en-1-one and 5,5-dibiphenylylcyclohexa-1,3-diene was studied to investigate the effect of having bichromophoric molecules with equal energy chromophores. In the first molecule, both the cyclohexenone and biphenyl moieties have triplet energies ca. 69 kcal/mole, and in the second molecule, both moieties have singlet energies ca. 95 kcal/mole.;For the diene system, up to five photoproducts were formed depending upon the photolysis conditions. The major products under all conditions were trans-5,6-dibiphenylylbicyclo 3.1.0 hex-2-ene and trans-4,5-dibipheylylbicyclo 3.1.0 hex-2-ene. This contrasts with the behavior of the phenyldiene where the major product depended upon the multiplicity of the excited state with the singlet giving electrocyclic ring opening and the triplet giving a di-pi-methane reaction.;Work was also done towards synthesizing molecular "rods" consisting of bicyclo 2.2.2 octane units bonded in a bridgehead to bridgehead manner with three or more "monomer" units. Success in synthesizing a 3 -rod was achieved using a magnesium - nickel(II) chloride promoted cross coupling reaction between bridgehead iodo- i - and 2 -rods, thus giving the first examples of rods greater than two units in length.;For the enone, three products were observed. These were the cis- and trans- isomers of 5,6-dibiphenylylcicyclo 3.1.0 hex-2-one and 3,4-dibiphenylylcyclohex-2-en-1-one. The quantum yields in benzene were 0.33 for the trans- product, 0.019 for the cis- product, and 0.013 for the 3,4-enone. Exothermic sensitization with xanthone (74 kcal/mole) and benzophenone (69 kcal/mole) gave the same quantum yields as the direct photolysis. Stern-Volmer quenching studies were done and gave a straight line. The rate of decay of the quenchable triplet was 5.7 x 10('8) sec('-1), which was 5.5-fold faster than the phenylenone. The operational rate of radiationless decay was 3.6 x 10('8) sec('-1), which was 2.3-fold than the phenylenone.
机译：研究了4,4-二联苯基苯基环己-2-烯-1和5,5-二联苯基环己-1,3-二烯的光化学，以研究具有相同能量发色团的双发色分子的作用。在第一个分子中，环己烯酮和联苯部分均具有大约三重态能量。 69 kcal / mole，并且在第二个分子中，两个部分都具有单重态能量。 95 kcal / mole .;对于二烯体系，取决于光解条件，最多可形成五种光产物。在所有条件下的主要产物是反式-5,6-二联苯基双环3.1.0己-2-烯和反式4,5-二联苯基双环3.1.0己-2-烯。这与苯二烯的行为形成对比，苯二烯的行为主要取决于激发态的多样性，其中单线态产生开环，三线态产生二-pi-甲烷反应。；还进行了合成分子“棒”的工作。由以桥头对桥头方式与三个或更多“单体”单元键合的双环2.2.2辛烷单元组成。使用氯化镁-镍（II）促进桥头碘-和2-杆之间的交叉偶联反应成功地合成了3-杆，从而给出了长度大于两个单位的杆的第一个示例。烯酮，观察到三种产物。它们是5，6-二联苯基基环3.1.0己-2-酮和3,4-二联苯基基环己-2-烯-1-酮的顺式和反式异构体。反式产物中苯的量子产率为0.33，顺式产物为0.019，3,4-烯酮为0.013。用x吨酮（74 kcal / mol）和二苯甲酮（69 kcal / mol）进行放热敏化得到与直接光解相同的量子产率。进行了斯特恩-沃尔默淬灭研究，并给出了一条直线。可淬灭三重态的衰变速率为5.7 x 10（'8）sec（'-1），比苯醌快5.5倍。无辐射衰变的工作速率为3.6 x 10（'8）sec（'-1），是苯醌的2.3倍。

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  • 作者

    KING, RUSSELL K.;

  • 作者单位

    The University of Wisconsin - Madison.;

  • 授予单位 The University of Wisconsin - Madison.;
  • 学科 Organic chemistry.
  • 学位 Ph.D.
  • 年度 1985
  • 页码 382 p.
  • 总页数 382
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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