Luminescent Zn(II) Coordination Polymers for Highly Selective Sensing of Cr(III) and Cr(VI) in Water
Luminescent Zn(II) Coordination Polymers for Highly Selective Sensing of Cr(III) and Cr(VI) in Water
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用于高选择性传感水中 Cr(III) 和 Cr(VI) 的发光 Zn(II) 配位聚合物
DOI：
10.1021/acs.inorgchem.7b00311
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发表时间：
2017-04-17
影响因子：
4.6
通讯作者：
Lang, Jian-Ping
中科院分区：
文献类型：
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作者：
Gu, Tian-Yi;Dai, Ming;Lang, Jian-Ping
三种光致发光锌配位聚合物{[Zn-2（tpeb）（2）（2，5-tdc）（2，5-Htdc）（2）].2H（2）0}（1），{[Zn-2（tpeb）（2）（1，4-ndc）（1，4-Hndc）（2）].2.6H（2）O}（n）（2）和{[Zn-2（tpeb）（2）（2，3-ndc）（2）]H2O}（n）（3）（TPEB = 1，3，5-三-4-吡啶基-1，2-乙烯基苯，2，5-TDC = 2，5-噻吩二甲酸，1，4-NDC = 1，4-萘二甲酸，2，3-NDC = 2，在溶剂热条件下，Zn（NO3）（2）.6H（2）O与tpeb和2，5-H（2）tdc、1，4-H（2）ndc或2，3-H（2）ndc反应，制备了3-（3-萘二甲酸）.化合物1具有通过2，5-tdc二价阴离子桥接1D [Zn（tpeb）]（n）链形成的二维（2D）网格状网络。2和3具有类似的一维（1D）双链结构，其衍生自通过成对的1，4-ndc或2，3-ndc配体桥接[Zn（tpeb）]（n）链。1-3的固态可见光发射被水中的Cr ~（3+）、CrO_（42-）和Cr_2 O_（72-）离子猝灭，最灵敏的配合物3的检测限为Cr ~（3+）0.88 ppb，Cr_2 O_（72-）2.623 ppb（pH = 3）或Cr_（42-）1.734 ppb（pH = 12）。这些数值远低于美国环保局和欧洲联盟设定的允许限值，也是迄今为止报告的双/三功能氯化石蜡传感器的最低值。Cr 3+发光猝灭的机制涉及不可逆的协调，以自由吡啶基网站的CP框架，而Cr 6+猝灭涉及可逆的重叠的分析物的吸收带与那些的激发和/或发射带为3。
Three photoluminescent zinc coordination polymers (CPs), {[Zn-2(tpeb)(2)(2,5-tdc)(2,5-Htdc)(2)].2H(2)0} (1), {[Zn-2(tpeb)(2)(1,4-ndc)(1,4-Hndc)(2)].2.6H(2)O}(n) (2), and {[Zn-2(tpeb)(2)(2,3-ndc)(2)]H2O}(n) (3) (tpeb = 1,3,5-tri-4-pyridy1-1,2-ethenylbenzene, 2,5-tdc = 2,5-thiophenedicarboxylic acid, 1,4-ndc = 1,4-naphthalenedicarboxylic acid, and 2,3-ndc = 2,3-naphthalenedicarboxylic acid) were prepared from reactions of Zn(NO3)(2).6H(2)O with tpeb and 2,5-H(2)tdc, 1,4-H(2)ndc, or 2,3-H(2)ndc under solvothermal conditions. Compound 1 has a two-dimensional (2D) grid-like network formed from bridging 1D [Zn(tpeb)](n) chains via 2,5-tdc dianions. 2 and 3 possess similar one-dimensional (1D) double-chain structures derived from bridging the [Zn(tpeb)](n) chains via pairs of 1,4-ndc or 2,3-ndc ligands. The solid-state, visible emission by 1-3 was quenched by Cr3+, CrO42-, and Cr2O72- ions in water with detection limits by the most responsive complex 3 of 0.88 ppb for Cr3+ and 2.623 ppb for Cr2O72- (pH = 3) or 1.734 ppb for CrO42- (pH = 12). These values are well below the permissible limits set by the USEPA and European Union and the lowest so far reported for any bi/trifunctional CPs sensors. The mechanism of Cr3+ luminescence quenching involves irreversible coordination to free pyridyl sites in the CP framework, while the Cr6+ quenching involves reversible overlap of the absorption bands of the analytes with those of the excitation and/or emission bands for 3.