Laboratory for Self-Assembly Chemistry, Department of Chemistry, Renmin University of China, Beijing 100872, People's Republic of China.
Inorg Chem. 2011 Jul 4;50(13):6055-62. doi: 10.1021/ic200047t. Epub 2011 Jun 9.
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) dimetallomacrocycles. Their structures were characterized by (1)H NMR and electrospray ionization mass spectrometry and in the cases of {(TMEDA)PdL(1)(2)}(NO(3))(4) (1), {(TMEDA)PdL(1)(2)}(PF(6))(4) (1a), and {(TMEDA)PdL(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)-type metallomacrocycles with NO(3)(-). The interactions between metallomacrocycles and various anions were investigated via fluorescence titration and cyclic voltammetry studies, respectively.
（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）和蒽或二茂铁基二咪唑配体（L（1-3））在水溶液中提供了一系列带正电荷的[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了表征，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）通过单晶 X 射线衍射分析进行了结构确证。有趣的是，1 和 1a 的 NMR 光谱表明，它们的结构差异在于，1 的一个 NO（3）（-）通过 C-H···O 氢键被包裹在篮形金属大环的空腔内，而 1a 的 PF（6）（-）则通过 C-H···F 氢键结合在外部。荧光滴定实验表明，基于蒽的带正电荷的[M（2）L（2）]（4+）型金属大环化合物与 NO（3）（-）形成了 1:1 的主客体络合。通过荧光滴定和循环伏安法研究分别研究了金属大环化合物与各种阴离子之间的相互作用。
