Two Dynamic ABW-Type Metal Organic Frameworks Built of Pentacarboxylate and Zn2+ as Photoluminescent Probes of Nitroaromatics
Two Dynamic ABW-Type Metal Organic Frameworks Built of Pentacarboxylate and Zn2+ as Photoluminescent Probes of Nitroaromatics
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两种由五羧酸盐和 Zn2 构建的动态 ABW 型金属有机框架作为硝基芳族化合物的光致发光探针
DOI：
10.1021/acs.cgd.6b00656
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发表时间：
2016-08-01
影响因子：
3.8
通讯作者：
Sun, Ying-Ji
中科院分区：
文献类型：
--
作者：
Di, Ling;Zhang, Jian-Jun;Sun, Ying-Ji
Zn ~（2+）与L ~ 5-（H_5L = 2，5-（6-（4-羧基苯胺基）-1，3，5-三嗪-2，4-二亚氨基）二对苯二甲酸）的自组装反应生成了两种新的ABW型沸石金属有机骨架（Z-MOFs）：（Me_2NH_2）[Zn ~ 2L]-3.5DMF（Me_2NH_2）[Zn ~ 2L（H_2O）]。2DMF-8H（2）O（2）（DMF = N，N-二甲基甲酰胺）。它们是由相同的五羧酸配体和金属离子构建的前两种Z-MOF：但哈弗两种构型和通道形状（分别为1和2的变形蜂窝状和人字形通道）。它们可以通过真空加热或在不同溶剂中浸泡来引发有趣的结构转变：虽然1和2之间的直接转变被证明是不可行的，但2可以首先转变为结晶中间体3，然后转变为1。此外，虽然2和3之间的转换是不可逆的，但1和3之间的转换是可逆的，伴随着它们的发射峰位置的26 nm的位移。与配体相比，化合物1、2和3的发光峰均发生蓝移，在固相和溶液相中均具有较强的蓝光发射。它们的光致发光被一系列硝基芳烃（NAC）溶液相和硝基苯（NB）蒸气有效和选择性地猝灭，使它们成为检测NAC的有希望的探针。1，3代表第一系列的MOFs作为有前途的光致发光探针检测地乐酚低至2.4 ppm。电子转移;骨架和NAC之间的长程能量转移和/或静电相互作用主要有助于猝灭机制。
Self-assembly reactions of Zn2+ and L5- (H5L = 2,5-(6-(4-carboxyphenylamino)-1,3,5-triazine-2,4-diyldiimino)diterephthalic acid)lead to the formation of two new ABW-type zeolitic metal-organic frameworks (Z-MOFs): (Me2NH2)[Zn2L]-3.5DMF (Me2NH2)[Zn2L(H2O)]. 2DMF-8H(2)O (2) (DMF = N,N-dimethylformamide). They are the first two Z-MOFs which are built of the same pentacarboxylate ligand and metal ion :but haver two configurations and channel shapes(distorted honeycomb and herringbone-shaped Channels for,1 and 2 respectively)., They can demonstrate interesting structural transformations triggered by vacuum heating or Soaking in different solvents: While direct transformations between 1 and 2 were revealed to be not feasible, 2 could be first transformed :to a crystalline intermediate 3 and then into 1. Furthermore, while transformations between 2 and 3 are irreversible, those between 1 and 3 are reversible, accompanied by a 26 nm shift of their emission peak positions. In comparison to the ligand, 1, 2, and 3 exhibit blue shifts in their luminescent emission peaks and have intensive blue emission in both Solid and "solution phases. The efficient and selective quenching of their photoluminescence by a series of nitroaromatics (NACs) solutions phase and by nitrobenzene (NB) vapor makes them promising probes for detecting NAcs. 1, 3 represent the first series of MOFs as promising photoluminescent probes for detecting dinoseb down to 2.4 ppm. The electron transfer; long-range energy transfer, and/or electrogtatic interactions between the frameworks and NACs mainly contribute to the quenching mechanisms.