College of Chemistry and Materials Science , Sichuan Normal University , Chengdu 610066 , P. R. China.
Institut de Chimie de Strasbourg , Centre National de la Recherche Scientifique (CNRS), UMR-7177, Université de Strasbourg , 4 rue Blaise Pascal , Strasbourg 67000 , France.
Inorg Chem. 2019 Dec 2;58(23):16040-16046. doi: 10.1021/acs.inorgchem.9b02548. Epub 2019 Nov 12.
When the reaction of zinc nitrate with 4',4‴,4‴″,4‴‴'-(ethene-1,1,2,2-tetrayl)tetrakis[(1,1'-biphenyl-3-carboxylic acid)] (Htmpe) in dimethylformamide (DMF) under hydrothermal condition is performed in air or carbon dioxide (CO), [Zn(tmpe)(HO)(μ-CO)]·8DMF·18HO () crystallizes out. However, if it is in dioxygen, argon, or carbon monoxide, [Zn(tmpe)(DMF)]·2DMF·8HO () is the product. Both compounds are chemically stable coordination polymers. contains zinc carboxylate paddlewheels as nodes linearly bridged by CO into two interpenetrating lattices, and has an infinite single framework formed by a tetranuclear node. is the second example containing the linear CO-bridged paddlewheel node. Interestingly, CO fixation in a μ-η bridging mode is observed in , which is rarely characterized structurally and has been confirmed using IR and gas chromatography analysis. The stability of is further verified by density functional theory calculations, which found an energy minimum with a Zn-O═C angle of 180°. Both compounds display strong emission around 490 nm and excited-state lifetimes around 2.4 ns.
当在水热条件下，硝酸锌与 4',4‴,4‴″,4‴‴'-(乙烯-1,1,2,2-四亚基)四[（1,1'-联苯-3-羧酸）]（Htmpe）在二甲基甲酰胺（DMF）中的反应在空气中或二氧化碳（CO）中进行时，[Zn(tmpe)(HO)(μ-CO)]·8DMF·18HO ()结晶出来。然而，如果在氧气、氩气或一氧化碳中，则生成[Zn(tmpe)(DMF)]·2DMF·8HO ()。这两种化合物都是化学稳定的配位聚合物。包含锌羧酸盐桨轮作为节点，通过 CO 线性桥接形成两个互贯晶格，而 具有由四核节点形成的无限单框架。是第二个包含线性 CO 桥接桨轮节点的例子。有趣的是，在 中观察到 μ-η 桥接模式的 CO 固定，这在结构上很少被表征，并通过 IR 和气相色谱分析得到证实。的稳定性进一步通过密度泛函理论计算得到验证，计算发现具有 180°Zn-O═C 角的能量最小值。这两种化合物在 490nm 左右均显示出强烈的发射，激发态寿命约为 2.4ns。
