State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, People's Republic of China.
Dalton Trans. 2018 Jun 5;47(22):7431-7444. doi: 10.1039/c8dt01299g.
This study reports the hydrothermal synthesis of a novel series of twelve coordination compounds, namely, {[Cd(μ-Hnbtc)(H2O)4]·H2O}n (1), [Zn2(μ-Hnbtc)2(phen)2]·2H2O (2), [Zn(Hnbtc)(phen)2(H2O)]·4.5H2O (3), [Ni(Hnbtc)(phen)2(H2O)]·6H2O (4), [Zn2(μ-Hnbtc)2(2,2'-bipy)2]·2H2O (5), [Cd3(μ5-nbtc)(μ6-nbtc)(2,2'-bipy)2(H2O)]n (6), {[Zn3(μ3-nbtc)2(phen)3(H2O)2]·4H2O} (7), [Co(H2O)6][Co2(nbtc)2(μ-4,4'-bipy)(4,4'-bipy)2(H2O)6]·8H2O (8), {[Ni3(μ4-nbtc)2(μ-4,4'-bipy)2.5(μ-H2O)(H2O)3]·4H2O}n (9), {[Cd2(μ4-nbtc)(μ-OH)(2,2'-bipy)2]·H2O}n (10), [Cd2(μ4-nbtc)(μ-OH)(phen)2(H2O)]n (11), and {[Zn2(μ5-nbtc)(μ3-OH)(μ-4,4'-bipy)]·4,4'-bipy·H2O}n (12), which are derived from 3'-nitro-biphenyl-2,4,4'-tricarboxylic acid (H3nbtc) as a virtually unexplored building block. These compounds were generated in aqueous medium from the corresponding metal(ii) chlorides as a metal source, H3nbtc as a principal building block, NaOH as a base, and simple N,N-donor aromatic ligands as crystallization mediators (i.e., 1,10-phenanthroline, phen; 2,2'-bipyridine, 2,2'-bipy; or 4,4'-bipyridine, 4,4'-bipy). All products 1-12 were completely characterized in the solid state by IR spectroscopy, elemental and thermogravimetric (TGA) analyses, powder (PXRD) and single-crystal X-ray diffraction. Structures of 1-12 range from discrete 0D dimers (2 and 5) or monomers (3, 4, and 8) to 1D coordination polymers (CPs, 1, 6, 7, 10, and 11) and 3D metal-organic frameworks (MOFs, 9 and 12). A broad structural diversity of 1-12 is guided by the type of the metal(ii) node, the molar ratio between H3nbtc and sodium hydroxide, and the kind of crystallization mediator. Topological analysis and classification of metal-organic underlying nets was made, disclosing the following topological types: 2C1 (in 1 and 7), 1M2-1 (in 2 and 5), SP1-periodic net (in 10 and 11), tfz-d (in 12), and some topologically unique nets (in 6 and 9). Luminescence behavior of 1-3, 5-7, and 10-12 was studied in the solid state. Magnetic properties of a Ni(ii) MOF 9 were also investigated and modeled. All obtained products 1-12 represent the first structurally characterized examples of coordination compounds derived from H3nbtc, thus opening up its application in coordination chemistry as a novel tricarboxylate building block.
本研究报告了一种新型系列十二配位化合物的水热合成，即[Cd(μ-Hnbtc)(H2O)4]·H2O(n=1)、[Zn2(μ-Hnbtc)2(phen)2]·2H2O(2)、[Zn(Hnbtc)(phen)2(H2O)]·4.5H2O(3)、[Ni(Hnbtc)(phen)2(H2O)]·6H2O(4)、[Zn2(μ-Hnbtc)2(2,2'-bipy)2]·2H2O(5)、[Cd3(μ5-nbtc)(μ6-nbtc)(2,2'-bipy)2(H2O)]n(6)、{[Zn3(μ3-nbtc)2(phen)3(H2O)2]·4H2O}(7)、[Co(H2O)6][Co2(nbtc)2(μ-4,4'-bipy)(4,4'-bipy)2(H2O)6]·8H2O(8)、{[Ni3(μ4-nbtc)2(μ-4,4'-bipy)2.5(μ-H2O)(H2O)3]·4H2O}n(9)、{[Cd2(μ4-nbtc)(μ-OH)(2,2'-bipy)2]·H2O}n(10)、[Cd2(μ4-nbtc)(μ-OH)(phen)2(H2O)]n(11)和{[Zn2(μ5-nbtc)(μ3-OH)(μ-4,4'-bipy)]·4,4'-bipy·H2O}n(12)，它们是由 3'-硝基联苯-2,4,4'-三羧酸（H3nbtc）作为一个几乎未被探索的构建块衍生而来的。这些化合物是在水溶液中由相应的金属（ii）氯化物作为金属源、H3nbtc 作为主要构建块、NaOH 作为碱和简单的 N，N-供体芳香配体作为结晶调节剂（即 1,10-菲咯啉、phen；2,2'-联吡啶、2,2'-bipy；或 4,4'-联吡啶、4,4'-bipy）生成的。所有产物 1-12 均通过红外光谱、元素和热重（TGA）分析、粉末（PXRD）和单晶 X 射线衍射在固态下完全表征。1-12 的结构范围从离散的 0D 二聚体（2 和 5）或单体（3、4 和 8）到 1D 配位聚合物（CPs，1、6、7、10 和 11）和 3D 金属-有机框架（MOFs，9 和 12）。1-12 的广泛结构多样性由金属（ii）节点的类型、H3nbtc 与氢氧化钠的摩尔比以及结晶调节剂的类型决定。对金属-有机基础网络进行了拓扑分析和分类，揭示了以下拓扑类型：2C1（在 1 和 7 中）、1M2-1（在 2 和 5 中）、SP1-周期性网络（在 10 和 11 中）、tfz-d（在 12 中）和一些拓扑独特的网络（在 6 和 9 中）。研究了 1-3、5-7 和 10-12 在固态下的发光行为。还研究了 Ni(ii)MOF 9 的磁性，并对其进行了建模。所有获得的产物 1-12 代表了第一个从 H3nbtc 衍生而来的配位化合物的结构特征实例，从而开辟了其作为新型三羧酸酯构建块在配位化学中的应用。
