Solution Self-Assembly, Spontaneous Deprotonation, and Crystal Structures of Bipyrazolate-Bridged Metallomacrocycles with Dimetal Centers

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• 作者：Shu-Yan Yu ; Hai-Ping Huang ; Sheng-Hui Li ; Qing Jiao ; Yi-Zhi Li ; Biao Wu ; Yoshihisa Sei ; Kentaro Yamaguchi ; Yuan-Jiang Pan ; and Hong-Wei Ma
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：December 12, 2005
• 年：2005
• 卷：44
• 期：25
• 页码：9471 - 9488
• 全文大小：548K
• 年卷期：v.44,no.25(December 12, 2005)
• ISSN：1520-510X

文摘

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 1, Pt 2; 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene),Pd 5; and 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbiphenyl, Pd 9], {[(phen)M]₈L₄}(NO₃)₈ [L = 3,3',5,5'-tetramethyl-4,4'-bipyrazolyl, Pd 3, Pt 4; 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, Pd 7; and 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbiphenyl, Pd 11], {[(bpy)Pd]₆L₃}(NO₃)₆ [L = 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, 6, 10], {[(phen)Pd]₆L₃}(NO₃)₆ [L = 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, 8, 12], {[(bpy)Pd]₄L₂}(NO₃)₄ [L = 1,3-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, 13, and 1,2-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, 15], and {[(phen)Pd]₄L₂}(NO₃)₄[L = 1,3-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, 14, and 1,2-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, 16] (wherebpy = 2,2'-bipyridine and phen = 1,10-phenanthroline) have been synthesized through a directed self-assemblyapproach 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 ¹³CNMR, cold-spray ionization or electrospray ionization mass spectrometry, UV-visible spectroscopy, and luminescencespectroscopy. Complexes 1, 3, 5, 6, 14, and 15 have also been characterized by single-crystal X-ray diffractionanalysis.