Yu Shu-Yan, Huang Hai-Ping, Li Sheng-Hui, Jiao Qing, Li Yi-Zhi, Wu Biao, Sei Yoshihisa, Yamaguchi Kentaro, Pan Yuan-Jiang, Ma Hong-Wei
State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, and Graduate School of the Chinese Academy of Sciences, Beijing 100080, People's Republic of China.
Inorg Chem. 2005 Dec 12;44(25):9471-88. doi: 10.1021/ic0509332.
A series of nanosized cavity-containing bipyrazolate-bridged metallomacrocycles with dimetal centers, namely, {[(bpy)M]8L4}(NO3)8 [L=3,3',5,5'-tetramethyl-4,4'-bipyrazolyl, Pd, Pt; 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene), Pd; and 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbiphenyl, Pd], {[(phen)M]8L4}(NO3)8 [L=3,3',5,5'-tetramethyl-4,4'-bipyrazolyl, Pd, Pt; 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, Pd; and 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbiphenyl, Pd], {[(bpy)Pd]6L3}(NO3)6 [L=1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,], {[(phen)Pd]6L3}(NO3)6 [L=1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,], {[(bpy)Pd]4L2}(NO3)4 [L=1,3-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, and 1,2-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,], and {[(phen)Pd]4L2}(NO3)4 [L=1,3-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, and 1,2-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,] (where bpy=2,2'-bipyridine and phen=1,10-phenanthroline) have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1H-bipyrazolyl ligands in aqueous solution. These complexes, with weak Pd(II)...Pd(II) or Pt(II)...Pt(II) interactions, have been characterized by elemental analysis, 1H and 13C NMR, cold-spray ionization or electrospray ionization mass spectrometry, UV-visible spectroscopy, and luminescence spectroscopy. Complexes and have also been characterized by single-crystal X-ray diffraction analysis.
通过一种定向自组装方法合成了一系列含纳米尺寸空腔的双吡唑盐桥联双金属中心金属大环化合物，即{[(bpy)M]8L4}(NO3)8 [L = 3,3',5,5'-四甲基-4,4'-双吡唑基，Pd，Pt；1,4-双-4'-(3',5'-二甲基)-吡唑基苯，Pd；以及1,4-双-4'-(3',5'-二甲基)-吡唑基联苯，Pd]，{[(phen)M]8L4}(NO3)8 [L = 3,3',5,5'-四甲基-4,4'-双吡唑基，Pd，Pt；1,4-双-4'-(3',5'-二甲基)-吡唑基苯，Pd；以及1,4-双-4'-(3',5'-二甲基)-吡唑基联苯，Pd]，{[(bpy)Pd]6L3}(NO3)6 [L = 1,4-双-4'-(3',5'-二甲基)-吡唑基苯]，{[(phen)Pd]6L3}(NO3)6 [L = 1,4-双-4'-(3',5'-二甲基)-吡唑基苯]，{[(bpy)Pd]4L2}(NO3)4 [L = 1,3-双-4'-(3',5'-二甲基)-吡唑基苯和1,2-双-4'-(3',5'-二甲基)-吡唑基苯]，以及{[(phen)Pd]4L2}(NO3)4 [L = 1,3-双-4'-(3',5'-二甲基)-吡唑基苯和1,2-双-4'-(3',5'-二甲基)-吡唑基苯]（其中bpy = 2,2'-联吡啶，phen = 1,10-菲咯啉），该方法涉及在水溶液中1H-双吡唑基配体的自发去质子化。这些配合物具有较弱的Pd(II)...Pd(II)或Pt(II)...Pt(II)相互作用，已通过元素分析、1H和13C NMR、冷喷雾电离或电喷雾电离质谱、紫外可见光谱和发光光谱进行了表征。配合物和还通过单晶X射线衍射分析进行了表征。
