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FUNCTIONALIZATION OF THE MOLECULE BY HYDROGEN BONDING AND PHOTOREACTION DYNAMICS

通过氢键和光反应动力学使分子功能化

基本信息

批准号：
10440166
负责人：
ARAI Tatsuo
金额：
$ 8.64万
依托单位：
UNIVERSITY OF TSUKUBA
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

The effect of inter- and intramolecular hydrogen bonding on the photochemical behaviors of aromatic compounds have been studied. Firstly, we have prepared a series of olefins with a pyrrole ring and a hetero aromatic ring such as pyridine or phenanthroline ring. In these olefins only the cis isomer forms intramolecular hydrogen bonding and showed intramolecular hydrogen atom transfer in the excited singlet state exhibiting fluorescence emission at considerably long wavelength region. Due to the hydrogen atom transfer only the trans→cis one-way photoisomerization has been observed. Secondly, we have revealed that intramolecular hydrogen bonding can control the efficiency and the mode of isomerization. Thus, 2'-hydroxychalcone, where both cis and trans isomers form 0-H : 0 intramolecular hydrogen bonding, exhibited intramolecular hydrogen atom transfer in the excited triplet state and finally resulted in one-way cis→trans isomerization around the C=C double bond. Thirdly, we have prepared a photochromic compound utilizing intramolecular hydrogen bonding exhibiting color change between reddish orange and greenish yellow by alternate irradiation with 366 nm and 546 nm light. Finally, we have prepared a series of donor-acceptor systems having 2-ureido-4 [1H]-pyrimidinone part which has very high association constant. In these systems photoinduced charge transfer interaction can take place even at very low concentration of the compounds by the aid of intramolecular hydrogen bonding.

研究了分子内和分子间氢键对芳香族化合物光化学行为的影响。首先，我们合成了一系列含吡咯环和杂芳环（如吡啶或菲咯啉环）的烯烃。在这些烯烃中，只有顺式异构体形成分子内氢键，并表现出分子内氢原子转移的激发单重态表现出荧光发射在相当长的波长区域。由于氢原子的转移，只观察到反式→顺式的单向光异构化。其次，我们揭示了分子内氢键可以控制异构化的效率和模式。因此，2 '-羟基查耳酮，其中顺式和反式异构体形成0-H：0分子内氢键，在激发三重态中表现出分子内氢原子转移，并最终导致围绕C=C双键的单向顺式→反式异构化。第三，我们已经制备了利用分子内氢键的光致变色化合物，其通过用366 nm和546 nm光交替照射而表现出红橙子和绿黄色之间的颜色变化。最后，我们制备了一系列具有很高缔合常数的2-脲基-4（1H）-嘧啶酮部分的给体-受体体系。在这些系统中，光诱导的电荷转移相互作用可以发生，即使在非常低的浓度的化合物通过分子内氢键的帮助。