Assembly of Binuclear, Tetranuclear, and Multinuclear Complexes from Pincer-Like Mononuclear Metallotectons: Structural Diversity Dependent on Precursors

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• 作者：Sheng-Run Zheng ; Mei Pan ; Kai Wu ; Ling Chen ; Ji-Jun Jiang ; Da-Wei Wang ; Jian-Ying Shi ; Cheng-Yong Su
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：February 4, 2015
• 年：2015
• 卷：15
• 期：2
• 页码：625-634
• 全文大小：580K
• ISSN：1528-7505

文摘

Reactions of Cu(II), Cd(II), and Ni(II) with a new tetradentate ligand N¹,N³-bis(1-(1H-benzimidazol-2-yl)ethylidene)propane-1,3-diamine (H₂bbepd) afforded four mononuclear pincer-like complexes of [Cu(H₂bbepd)(ClO₄)]路CH₃OH路ClO₄ (1), [Cd(H₂bbepd)(CH₃OH)(ClO₄)]路CH₃OH路ClO₄ (2), [Ni(H₂bbepd)(H₂O)₂]路2ClO₄ (3), and [Ni(H₂bbepd)(NO₃)₂] (4), respectively. The labile small coordinated components (anions or solvent molecules) on the apical coordination site of metal ions in complexes 1鈥?b>4 display three different modes, which can be substituted by 4,4鈥?bipyridine (bpy) to obtain four new multinuclear complexes of [Cu₂(H₂bbepd)₂(bpy)]₂路4ClO₄ (5), [Cd₄(H₂bbepd)₄(bpy)₃(ClO₄)₂]路6ClO₄路(bpy)路2CH₃OH路6H₂O (6), {[Ni(H₂bbepd)(bpy)]路2ClO₄路CH₃OH}_n (7), and {[Ni (H₂bbepd)(bpy)]路2NO₃路CH₃OH路H₂O}_n (8), respectively. Complex 5 is a binuclear dumbbell-like molecule, complex 6 is a rare example of discrete linear tetranuclear molecule, while complexes 7 and 8 are one-dimensional chains formed by an alternate arrangement of bpy molecules and mononuclear subunits. The differences in complexes 5鈥?b>8 are largely dependent on the structure of the mononuclear precusors of complexes 1鈥?b>4. All eight complexes are assembled into higher dimensional supramolecular frameworks by diverse nonconvalent interactions including unusual anion路路路蟺 interactions between perchlorate and five-membered benzimidazole rings.