Synthesis and anion sensing of water-soluble metallomacrocycles.
Synthesis and anion sensing of water-soluble metallomacrocycles.
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DOI：
10.1021/ic200047t
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发表时间：
2011-06
影响因子：
4.6
通讯作者：
L. Yao;Lin Qin;Ting-Zheng Xie;Yi-zhi Li;Shu‐Yan Yu
中科院分区：
文献类型：
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作者：
L. Yao;Lin Qin;Ting-Zheng Xie;Yi-zhi Li;Shu‐Yan Yu
（TMEDA）Pd（NO（3））（2）或（TMEDA）Pt（NO（3））（2）（其中TMEDA = N（1），N（1），N（2），N（2）-四甲基乙烷-1，2-二胺）与蒽基或二茂铁基二咪唑配体（L（1-3））在水溶液中自组装得到一系列带正电荷的[M（2）L（2）]（4+）二金属大环化合物.它们的结构通过（1）H NMR和电喷雾电离质谱进行表征，并且对于{[（TMEDA）Pd]（2）L（1）（2）}（NO（3））（4）（1）、{[（TMEDA）Pd]（2）L（1）（2）}（PF（6））（4）（1a）和{[（TMEDA）Pd]（2）L（3）（2）}（NO（3））（4）（4）的情况，通过单晶X射线衍射分析进行表征。有趣的是，1和1a的NMR谱揭示了它们的结构差异，X射线衍射分析证实，1的NO（3）（-）通过C-H···O氢键包封在篮状金属大环的空腔内，而1a的PF（6）（-）通过C-H···F氢键结合在外侧。荧光滴定实验表明，蒽基带正电荷的[M（2）L（2）]（4+）型金属大环化合物与NO（3）（-）形成1：1的主客体络合物.用荧光滴定法和循环伏安法研究了金属大环化合物与不同阴离子的相互作用。
The self-assembly of (TMEDA)Pd(NO(3))(2) or (TMEDA)Pt(NO(3))(2) (where TMEDA = N(1),N(1),N(2),N(2)-tetramethylethane-1,2-diamine) and anthracene- or ferrocene-based diimidazole ligands (L(1-3)) in aqueous solution affords a series of positively charged [M(2)L(2)](4+) dimetallomacrocycles. Their structures were characterized by (1)H NMR and electrospray ionization mass spectrometry and in the cases of {[(TMEDA)Pd](2)L(1)(2)}(NO(3))(4) (1), {[(TMEDA)Pd](2)L(1)(2)}(PF(6))(4) (1a), and {[(TMEDA)Pd](2)L(3)(2)}(NO(3))(4) (4) by single-crystal X-ray diffraction analysis. Interestingly, the NMR spectra of 1 and 1a revealed that the difference of their structures, as confirmed by X-ray diffraction analysis, was that a NO(3)(-) of 1 was encapsulated inside the cavity of the basket-shaped metallomacrocycle by C-H···O hydrogen bonds, while PF(6)(-) of 1a was bound outside by C-H···F hydrogen bonds. The fluorescence titration experiment exhibited the formation of 1:1 host-guest complexation for anthracene-based positively charged [M(2)L(2)](4+)-type metallomacrocycles with NO(3)(-). The interactions between metallomacrocycles and various anions were investigated via fluorescence titration and cyclic voltammetry studies, respectively.