ALL-OR-NONE TYPE PHOTOCHEMICAL SWITCHING OF CATION BINDING WITH MALACHITE GREEN CARRYING A BIS(MONOAZACROWN ETHER) MOIETY
ALL-OR-NONE TYPE PHOTOCHEMICAL SWITCHING OF CATION BINDING WITH MALACHITE GREEN CARRYING A BIS(MONOAZACROWN ETHER) MOIETY
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带有双(单氮杂冠醚)部分的孔雀石绿阳离子结合的全或全型光化学转换
DOI：
10.1021/ja963405l
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发表时间：
1997
期刊：
影响因子：
--
通讯作者：
H. Doe
中科院分区：
文献类型：
--
作者：
K. Kimura;Ryoko Mizutani;M. Yokoyama;R. Arakawa;G. Matsubayashi;M. Okamoto;H. Doe
引入光致变色基团的冠醚衍生物，我们称之为光致变色冠醚，是光化学控制金属离子结合的有吸引力的工具。1-5例如，偶氮苯部分，其光化学异构化之间的反式和顺式的形式，可以用于改变双（冠醚）的configuration 6和穴状配体7的空腔大小光异构化。在经历其电中性螺吡喃形式和两性离子mercuryone之间的光异构化的冠状螺苯并吡喃中，其阳离子结合能力可以通过由其冠醚部分络合的金属离子和mercuryone形式的酚盐阴离子之间的分子内相互作用进行光化学控制。8，9在光致变色冠醚阳离子结合的光控系统中，它利用冠醚拓扑结构的光致变化，只能实现适度的高和低阳离子结合能力之间的适度变化;阳离子络合常数为0或接近0的任何状态都很难达到。阳离子结合中的这些适度的光诱导变化对于将光致变色冠醚应用于需要在1和0位之间，即在“全部”和“无”状态之间进行明确切换的切换器件是不方便的。我们已经设计了带有孔雀石绿色亮腈部分的苯并冠醚（1），该部分在紫外光照射下在分子间电离，针对基于静电排斥的光诱导阳离子释放。在冠状孔雀石绿色中，由于所得醌型阳离子与通过其冠醚部分络合的金属离子之间的静电排斥，预期有效的阳离子释放。然而，电位测量表明，光离子-
Crown ether derivatives incorporating a photochromic moiety, what we call photochromic crown ethers, are attractive tools for photochemical control of metal ion binding. 1-5 For instance, the azobenzene moiety, which isomerizes photochemically between its trans and cis forms, can be used for changing the bis (crown ether) configuration6 and the cryptand7 cavity sizes upon photoisomerization. In a crowned spirobenzopyran which undergoes photoisomerization between its electrically neutral spiropyran form and zwitterionic merocyanine one, its cationbinding ability can be controlled photochemically by intramolecular interaction between a metal ion complexed by its crown ether moiety and the phenolate anion in the merocyanine form. 8, 9 In the photocontrol systems of cation binding by photochromic crown ethers, which take advantage of photoinduced changes in the topology of crown ethers, only modest changes between the moderately high and low cation-binding abilities can be realized; any state for cation complexation constants of 0 or nearly 0 can hardly be attained. These modest photoinduced changes in the cation binding is inconvenient for application of the photochromic crown ethers to switching devices that require clear-cut switching between 1 and 0 digits, that is, between “all” and “none” states.We have already designed a benzocrown ether (1) carrying a malachite green leuconitrile moiety that ionizes intermolecularly upon UV-light irradiation, aiming at photoinduced cation release based on electrostatic repulsion. 10, 11 In the crowned malachite green, efficient cation release was expected due to the electrostatic repulsion between the resulting quinoid cation and metal ion complexed by its crown ether moiety. Potentiometric measurements, however, suggested that the photoion-