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2,3-二羧基-双环[2.2.1]2,5-庚二烯价键异构化反应的研究
引用本文:孟宪娟,明阳福,樊美公. 2,3-二羧基-双环[2.2.1]2,5-庚二烯价键异构化反应的研究[J]. 影像科学与光化学, 1993, 11(2): 36-39. DOI: 10.7517/j.issn.1674-0475.1993.02.36
作者姓名:孟宪娟  明阳福  樊美公
作者单位:中国科学院感光化学研究所, 北京 100101
摘    要:以聚四苯基卟啉(P-TPP)为敏化剂,研究了2,3-二羧基-双环[2.2.1]-2,5-庚二烯(N)的光化学价键异构化反应,在0.1mol/L的碳酸钠甲醇溶剂中,在适量的P-TPP存在下,可见光照射时,N可以定量地转化为2,3-二羧基四环[2.2.1.02,6.03,5]庚烷(Q),Q在聚四苯基卟啉钴络合物(Co-P-TPP)催化剂的作用下,又可定量地异构化返回N.分别研究了敏化剂和催化剂用量对反应的影响。通过反应物之间激发态能量的比较及N对P-TPP荧光的猝灭试验,证明光异构化反应是通过电子转移反应机制进行的。

关 键 词:价键异构  光敏化  聚四苯基卟啉  2  3-二羧基-双环[2.2.1]-2  5-庚二烯  
收稿时间:1992-04-27

STUDY ON PHOTOCHEMICAL VALENCE ISOMERIZATION OF BICYCLO-[2.2.1]-2,3-DICARBOXY-2, 5-HEPTADIENE
MENG XIAN-JUAN,MING YANG-FU,FAN MEI-GONG. STUDY ON PHOTOCHEMICAL VALENCE ISOMERIZATION OF BICYCLO-[2.2.1]-2,3-DICARBOXY-2, 5-HEPTADIENE[J]. Imaging Science and Photochemistry, 1993, 11(2): 36-39. DOI: 10.7517/j.issn.1674-0475.1993.02.36
Authors:MENG XIAN-JUAN  MING YANG-FU  FAN MEI-GONG
Affiliation:Institute of Photographic Chemistry, Academia Sinica, Beijing 100101, P.R. China
Abstract:Photochemical valence isomerization of bicyclo [2. 2. 1] -2, 3 -dicarboxy -2, 5 -heptadiene (N) to quadrocyclo[2.2.1.02,3. 05,6]-2, 3 - dicarboxy heptane (Q) was performed by using polytetraphenyl-porphrine(P-TPP)as sensitizer. In addition, The Q can be easily converted into N under the presence of catalyst, Cobalt (Ⅱ) polytetraphenylpor-phrine (Co-P-TPP). The effects of the sensitizer and the catalyst on these isomerization reaction were tested. The comparation between the excited state energy of P - TPP and N indicated that photochemical valence isomerization may go by way of electron transfer from P-TPP to N. The support for the electron transfer machenism is fluorescence quenching of P-TPP by N.
Keywords:valence isomerization  photosensitized reaction  polytetraphenylpor-phrine  bicyclo[2.2.1]-2  3-dicatboxy-2  5-heptadiene  
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