Gu Tian-Yi, Dai Ming, Young David James, Ren Zhi-Gang, Lang Jian-Ping
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, People's Republic of China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032, People's Republic of China.
Inorg Chem. 2017 Apr 17;56(8):4669-4679. doi: 10.1021/acs.inorgchem.7b00311. Epub 2017 Mar 24.
Three photoluminescent zinc coordination polymers (CPs), {[Zn(tpeb)(2,5-tdc)(2,5-Htdc)]·2HO} (1), {[Zn(tpeb)(1,4-ndc)(1,4-Hndc)]·2.6HO} (2), and {[Zn(tpeb)(2,3-ndc)]·HO} (3) (tpeb = 1,3,5-tri-4-pyridyl-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(NO)·6HO with tpeb and 2,5-Htdc, 1,4-Hndc, or 2,3-Hndc under solvothermal conditions. Compound 1 has a two-dimensional (2D) grid-like network formed from bridging 1D [Zn(tpeb)] chains via 2,5-tdc dianions. 2 and 3 possess similar one-dimensional (1D) double-chain structures derived from bridging the [Zn(tpeb)] chains via pairs of 1,4-ndc or 2,3-ndc ligands. The solid-state, visible emission by 1-3 was quenched by Cr, CrO, and CrO ions in water with detection limits by the most responsive complex 3 of 0.88 ppb for Cr and 2.623 ppb for CrO (pH = 3) or 1.734 ppb for CrO (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 Cr luminescence quenching involves irreversible coordination to free pyridyl sites in the CP framework, while the Cr quenching involves reversible overlap of the absorption bands of the analytes with those of the excitation and/or emission bands for 3.
通过在溶剂热条件下使硝酸锌六水合物（Zn(NO₃)₂·6H₂O）与1,3,5 - 三（4 - 吡啶基）- 1,2 - 乙烯基苯（tpeb）以及2,5 - 噻吩二甲酸（2,5 - tdc）、1,4 - 萘二甲酸（1,4 - ndc）或2,3 - 萘二甲酸（2,3 - ndc）反应，制备了三种光致发光锌配位聚合物（CPs），即{[Zn(tpeb)(2,5 - tdc)(2,5 - Htdc)]·2H₂O}（1）、{[Zn(tpeb)(1,4 - ndc)(1,4 - Hndc)]·2.6H₂O}（2）和{[Zn(tpeb)(2,3 - ndc)]·H₂O}（3）。化合物1具有由二维（2D）网格状网络构成，该网络通过2,5 - tdc二价阴离子桥连一维[Zn(tpeb)]链形成。化合物2和3具有类似的一维（1D）双链结构，这些结构通过1,4 - ndc或2,3 - ndc配体对桥连[Zn(tpeb)]链得到。1 - 3在固态下的可见光发射会被水中的Cr³⁺、Cr₂O₇²⁻和CrO₄²⁻离子猝灭，对于最灵敏的配合物3而言，对Cr³⁺的检测限为0.88 ppb，对pH = 3时的Cr₂O₇²⁻为2.623 ppb，对pH = 12时的CrO₄²⁻为1.734 ppb。这些值远低于美国环境保护局（USEPA）和欧盟设定的允许限值，并且是目前报道的任何双/三功能CPs传感器中最低的。Cr³⁺发光猝灭的机制涉及与CP框架中游离吡啶基位点的不可逆配位，而Cr₂O₇²⁻猝灭涉及分析物的吸收带与3的激发和/或发射带的吸收带的可逆重叠。
