(1,6)Pyrenophanes containing crown ether moieties as fluorescence sensors for metal and ammonium ions. Formation of sandwich, dumbbell, and pseudorotaxane complexes
(1,6)Pyrenophanes containing crown ether moieties as fluorescence sensors for metal and ammonium ions. Formation of sandwich, dumbbell, and pseudorotaxane complexes
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(1,6)含有冠醚部分的吡咯啉作为金属和铵离子的荧光传感器。
DOI：
10.1039/d2nj04790j
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发表时间：
2023
影响因子：
3.3
通讯作者：
Masahito Segi
中科院分区：
文献类型：
--
作者：
Hajime Maeda;Genki Saito;Taniyuki Furuyama;Masahito Segi
（1，6）合成了芘的1，6-位分别与三乙二醇和四乙二醇链桥连的芘番1和2。将Ba（ClO 4）2加入到10−5 M CH 2Cl 2：CH 3CN = 1：1的1溶液中，分子内激基缔合物发射在480 nm处最大，而单体发射在370-400 nm处增加。 与此相反，添加Ba（ClO 4）2的2的溶液中移动的分子内激基缔合物发射到较短的波长。加入n-Bu 2NH 2 + PF 6 −后，化合物1和2的分子内激基缔合物发射均减弱，单体发射增强。根据这些荧光变化的结果，Job的图，和NMR滴定，它的结论是，1形成1：1的双金属型配合物与Ba 2+，2形成1：2的哑铃型配合物与Ba 2+，和1和2形成伪轮烷与n-Bu 2NH 2+。 研究还发现，当芘番1和2与四氰基乙烯（TCNE）在二氯甲烷中混合时，形成电荷转移（CT）复合物，其最大吸收波长分别为740和744 nm。
(1,6)Pyrenophanes 1 and 2 in which 1,6-positions of pyrene are bridged with respective tri- and tetra-ethylene glycol chains were synthesized. Addition of Ba(ClO4)2 to a 10−5 M CH2Cl2 : CH3CN = 1 : 1 solution of 1 reduced the intramolecular excimer emission with a maximum at 480 nm and increased the monomer emission around 370–400 nm. In contrast, addition of Ba(ClO4)2 to the solution of 2 shifted the intramolecular excimer emission to shorter wavelengths. Addition of n-Bu2NH2+PF6− to the solutions of 1 and 2 both decreased the intramolecular excimer emission and increased the monomer emission. Based on the results of these fluorescence changes, Job's plots, and NMR titration, it is concluded that 1 forms a 1 : 1 sandwich-type complex with Ba2+, 2 forms a 1 : 2 dumbbell-type complex with Ba2+, and both 1 and 2 form pseudorotaxanes with n-Bu2NH2+. It was also found that when the pyrenophanes 1 and 2 were mixed with tetracyanoethylene (TCNE) in CH2Cl2, charge-transfer (CT) complexes were formed, that exhibited absorption maxima at 740 and 744 nm, respectively.