External Template-Assisted Self-Assembly:Design and Synthesis of 4,4鈥?bipy-Based Mo(W)/Cu/S Heterothiometallic Polymeric Clusters Directed by 1,1鈥?Bis(pyridinium)methylene Cation

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• 作者：Yi Han ; Zhenhua Zhang ; Yanyan Liu ; Yunyin Niu ; Degang Ding ; Benlai Wu ; Hongwei Hou ; Yaoting Fan
• 刊名：Crystal Growth & Design
• 出版年：2011
• 出版时间：August 3, 2011
• 年：2011
• 卷：11
• 期：8
• 页码：3448-3455
• 全文大小：1016K
• 年卷期：v.11,no.8(August 3, 2011)
• ISSN：1528-7505

文摘

Organic cation-templated self-assembly of 4,4鈥?bipy (4,4鈥?bipy = bpy) with [NH₄]₂MS₂O₂ (M = Mo, W) and CuX (X = Cl, NCS) in the present of 1,1-bis(pyridinium)methylene [bpm = 1,1鈥?bis(pyridinium)methylene] resulted in four novel neutral heterothiometallic cluster polymers based on tetranuclear [Mo/WOS₃Cu₃] unit: [MOS₃Cu₃Cl(渭-bpy)₂路Sol]_n (M = Mo, Sol = 1.3DMF路5.5H₂O 1; M = W, Sol = 1.5DMF路8.2H₂O 2), [MoOS₃Cu₃(NCS)(bpy)(渭-bpy)₂路DMF]_n (3), and [WOS₃Cu₃(NCS)(渭-bpy)_2.5路3DMF]_n (4). Polymer 1 or 2 crystallizes in the Fddd space group with a 2-fold interpenetrating (10,3)-b net, which presents a 3-connected 3D heterothiometallic polymer assembled with bidentate organic bridging ligands. Polymer 3 crystallizes in the space group P1 with a 2D noninterpenetrating network with (6,3) topology in which [MoOS₃Cu₃(bpy)] units are interconnected via three single or double Cu-渭-bpy-Cu bridges. Polymer 4 crystallizes in the space group C2/c with a (6⁴ 8²) net, which displays the first self-interpenetrating network in heterothiometallic chemistry. All of these results confirm the ideal template effect and correct choice of bpm.