Synthesis of double-armed lariat ethers with pyrene moieties at each end of two sidearms and their fluorescence properties in the presence of alkali metal and alkaline earth metal cations.
Synthesis of double-armed lariat ethers with pyrene moieties at each end of two sidearms and their fluorescence properties in the presence of alkali metal and alkaline earth metal cations.
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DOI：
10.1021/jo0498056
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发表时间：
2004-06
期刊：
影响因子：
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通讯作者：
Yoshio Nakahara;T. Kida;Y. Nakatsuji;M. Akashi
中科院分区：
文献类型：
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作者：
Yoshio Nakahara;T. Kida;Y. Nakatsuji;M. Akashi
合成了两种类型的在两个侧臂的每个末端具有芘部分的双臂丙醚衍生物，（3x + 1）-冠-x衍生物1（x = 5）、2（x = 6）和3（x = 4）（A型）和3 y-冠-y衍生物6（y = 5）和7（y = 6）（B型），用荧光光谱法研究了它们对碱金属和碱土金属阳离子的络合行为。芘激基缔合物发射下降的同时，在金属离子络合的单体发射增加。这一发现归因于两个芘环的空间距离的变化的运动抑制的冠环和两个侧臂的基础上与金属阳离子络合。对碱土金属阳离子的选择性高度依赖于主体空腔的适合度和客体的大小。虽然大多数荧光团对碱金属离子没有反应，但只有含有18-冠-6环的反式-7a显示出K（+）选择性。
Two types of double-armed lariat ether derivatives having pyrene moieties at each end of two sidearms, (3x + 1)-crown-x derivatives 1 (x = 5), 2 (x = 6), and 3 (x = 4) (type A) and 3y-crown-y derivatives, 6 (y = 5) and 7 (y = 6) (type B), were synthesized, and their complexation behavior toward alkali metal and alkaline earth metal cations was examined by fluorescence spectroscopy. Pyrene excimer emission decreased accompanied by an increase in monomer emission upon metal ion complexation. This finding is ascribed to the change of the spatial distance of two pyrene rings by movement suppression of both the crown ring and one of the two sidearms based on complexation with the metal cation. The selectivity for alkaline earth metal cations was highly dependent on the fitness of the host cavity and the guest size. Although most of the fluorophores did not respond to alkali metal cations, only trans-7a containing an 18-crown-6 ring showed K(+) selectivity.