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Metal–organic architectures designed from a triphenyl-pentacarboxylate linker: hydrothermal assembly, structural multiplicity, and catalytic Knoevenagel condensation
Inorganic Chemistry Frontiers ( IF 7 ) Pub Date : 2021-07-19 , DOI: 10.1039/d1qi00680k
Hong-Rui Zhang 1, 2, 3, 4 , Jin-Zhong Gu 2, 3, 5, 6, 7 , Marina V. Kirillova 8, 9, 10, 11, 12 , Alexander M. Kirillov 8, 9, 10, 11, 12
Affiliation  

A triphenyl-pentacarboxylic acid, 3,5-di(2′,4′-dicarboxylphenyl)benzoic acid (H5ddba), was applied as an adaptable linker for the hydrothermal assembly of eight new metal(II) coordination polymers (CPs) and complexes, formulated as [Cu2(μ-H3ddba)2(phen)2] (1), {[Cd24-Hddba)(phen)2(H2O)2]·2H2O}n (2), [M43-Hddba)2(2,2′-bipy)6(μ-H2O)]·6H2O (M = Ni (3), Mn (4)), {[Co25-Hddba)(μ-4,4′-bipy)1.5(H2O)]·H2O}n (5), {[Zn25-Hddba)(4,4′-bipy)1.5]·4,4′-bipy·2H2O}n (6), [Mn26-Hddba)(H2biim)(H2O)]n (7), and {[Cd27-ddba)(Hbpa)]·5H2O}n (8). The products 1–8 were generated from metal(II) chlorides, H5ddba, and various N-donor supporting ligands acting as mediators of crystallization (i.e., phen: 1,10-phenanthroline; 2,2′-bipy: 2,2′-bipyridine; 4,4′-bipy: 4,4′-bipyridine; H2biim: 2,2′-biimidazole; or bpa: bis(4-pyridyl)amine). All compounds were analyzed by standard methods (C/H/N analysis, FTIR, TGA and PXRD) including single-crystal X-ray diffraction. The structural multiplicity of 1–8 ranges from discrete dimers (1) or tetramers (3 and 4) to a 1D coordination polymer (2) and 3D metal–organic frameworks (5–8). Topological analysis of simplified H-bonded or metal–organic networks disclosed fcu (1), 2C1 (2), dia (3 and 4), sra (6), 3,4,7T3 (8), and unprecedented (5 and 7) topologies. The catalytic activity of 1–8 was investigated in a model Knoevenagel condensation between benzaldehydes and malononitrile, resulting in up to 99% yields of condensation products. The substrate scope, catalyst recycling, and effects of different reaction parameters were investigated. Finally, this work extends the use of H5ddba as an aromatic pentacarboxylate building block for the design of new metal–organic architectures with captivating structures and functional properties.

中文翻译:

由三苯基-五羧酸酯连接体设计的金属-有机结构:水热组装、结构多样性和催化 Knoevenagel 缩合

三苯基五羧酸、3,5-二(2',4'-二羧基苯基)苯甲酸 (H 5 ddba) 被用作八种新型金属 ( II ) 配位聚合物 (CP)的水热组装的适应性接头和配合物,公式为 [Cu 2 (μ-H 3 ddba) 2 (phen) 2 ] ( 1 ), {[Cd 24 -Hddba)(phen) 2 (H 2 O) 2 ]·2H 2 O } n ( 2 ), [M 43 -Hddba) 2 (2,2'-bipy) 6 (μ-H 2O)]·6H 2 O (M = Ni ( 3 ), Mn ( 4 )), {[Co 25 -Hddba)(μ-4,4'-bipy) 1.5 (H 2 O)]·H 2 O} n ( 5 ), {[Zn 25 -Hddba)(4,4'-bipy) 1.5 ]·4,4'-bipy·2H 2 O} n ( 6 ), [Mn 26 -Hddba)(H 2 biim)(H 2 O)] n ( 7 ),和{[Cd 27 -ddba)(Hbpa)]·5H 2O} n ( 8 )。产物1-8由金属 ( II ) 氯化物、H 5 ddba 和作为结晶介质的各种 N-供体支持配体(phen: 1,10-phenanthroline; 2,2'-bipy: 2, 2'-联吡啶;4,4'-联吡啶:4,4'-联吡啶;H 2 biim:2,2'-联咪唑;或 bpa:双(4-吡啶基)胺)。所有化合物均通过标准方法(C/H/N 分析、FTIR、TGA 和 PXRD)进行分析,包括单晶 X 射线衍射。1-8的结构多样性范围从离散的二聚体 ( 1 ) 或四聚体 ( 34 ) 到一维配位聚合物 (2 ) 和 3D 金属-有机框架 ( 5-8 )。简化H-粘结或金属-有机网络拓扑分析公开FCU1),2C1(2),直径34),SRA6),3,4,7T3(8),和前所未有(57 ) 拓扑。1-8的催化活性在苯甲醛和丙二腈之间的 Knoevenagel 缩合模型中进行了研究,导致缩合产物的产率高达 99%。研究了底物范围、催化剂回收和不同反应参数的影响。最后,这项工作扩展了 H 5 ddba 作为芳香族五羧酸盐结构单元的用途,用于设计具有迷人结构和功能特性的新型金属-有机结构。
更新日期:2021-08-09
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