Yeh Chuan-Heng, Tsai Meng-Jung, Lee Pei-Chin, Wu Jing-Yun
Department of Applied Chemistry, National Chi Nan University, Nantou 545, Taiwan.
Inorg Chem. 2023 Aug 21;62(33):13453-13466. doi: 10.1021/acs.inorgchem.3c01800. Epub 2023 Aug 9.
The reactions of Zn(NO), 3,6-(pyridin-3-yl)-9-carbazole (bpycz), and 2,5-dihydroxyterephthalic acid (Hdhbdc) or 2-bromoterephthalic acid (Br-1,4-Hbdc) under hydro(solvo)thermal conditions yielded corresponding coordination polymers (CPs) {[Zn(Hdhbdc)(bpycz)]•0.5HO} () and [Zn(Br-1,4-bdc)(bpycz)]•2DMAc•HO (), respectively, with high thermal stability approaching 350 °C. CP adopts a ring-and-rod layer structure, which is topologically described as a 4-connected net with the point symbol of 2•6. Two layers are interpenetrated in parallel interlocking mode to form a double 2D → 2D polyrotaxane entanglement with extra-framework void space of 19.6%. CP has a non-interpenetrating ring-and-rod layer structure of 4-connected 2•6 net topology, with extra-framework void space of 16.6%. Thermally activated and revealed CO uptakes of 101.1 and 98.6 cm g, respectively, at / = 1 and 195 K. X-ray powder diffraction (XRPD) patterns confirmed that and both possessed high chemical stability in HO, CHOH, acetone, and DMF, and framework stability during gas adsorption-desorption. The HO suspension of displayed excitation-dependent dual-emissive properties, appearing at 432 nm upon excitation at 300 nm and at 528 nm upon excitation at 365 nm. Of note, was capable of detection of Fe, Cr, and Al ions in HO, showing good anti-interference ability, excellent selectivity, and high sensitivity. More interesting, the dual-emissive properties make to be an excellent luminescence chemosensor to screen Fe, Cr, and Al from a pool of metal ions in HO upon excitation at 300 nm via luminescence quenching effect and then discriminate Fe, Cr, and Al upon excitation at 365 nm via luminescence quenching, unaltered, and enhancement responses, respectively. On the other hand, the HO suspension of demonstrated an excitation-independent emission appearing at around 430 nm, which could be utilized to sensitively detect Fe and Cr ions with good anti-interference ability and excellent selectivity via luminescence quenching effect. Further, and were recyclability and possessed cycling stability. The plausible sensing mechanisms for and toward Fe, Cr, and Al were also explored in detail.
在水（溶剂）热条件下，硝酸锌、3,6 -（吡啶 - 3 - 基）- 9 - 咔唑（bpycz）与2,5 - 二羟基对苯二甲酸（Hdhbdc）或2 - 溴对苯二甲酸（Br - 1,4 - Hbdc）反应，分别生成了相应的配位聚合物（CPs）{[Zn(Hdhbdc)(bpycz)]•0.5H₂O}（）和[Zn(Br - 1,4 - bdc)(bpycz)]•2DMAc•H₂O（），它们具有接近350℃的高热稳定性。CP 采用环棒层结构，拓扑结构上被描述为具有点符号2•6的4 - 连接网络。两层以平行互锁模式相互贯穿，形成双二维→二维聚轮烷缠结，框架外空隙空间为19.6%。CP 具有4 - 连接2•6网络拓扑的非互穿环棒层结构，框架外空隙空间为16.6%。热活化后的 和 在p/p₀ = 1和195 K时，CO吸附量分别为101.1和98.6 cm³ g⁻¹。X射线粉末衍射（XRPD）图谱证实 和 在H₂O、CH₃OH、丙酮和DMF中都具有高化学稳定性，以及在气体吸附 - 解吸过程中的框架稳定性。 的H₂O悬浮液表现出激发依赖的双发射特性，在300 nm激发时出现在432 nm，在365 nm激发时出现在528 nm。值得注意的是， 能够检测H₂O中的Fe、Cr和Al离子，显示出良好的抗干扰能力、优异的选择性和高灵敏度。更有趣的是，双发射特性使 成为一种出色的发光化学传感器，通过在300 nm激发时的发光猝灭效应从H₂O中的金属离子池中筛选出Fe、Cr和Al，然后在365 nm激发时分别通过发光猝灭、不变和增强响应来区分Fe、Cr和Al。另一方面， 的H₂O悬浮液表现出在430 nm左右的激发不依赖发射，可通过发光猝灭效应灵敏地检测Fe和Cr离子，具有良好的抗干扰能力和优异的选择性。此外， 和 具有可回收性并具备循环稳定性。还详细探索了 和 对Fe、Cr和Al的可能传感机制。
