Yu Xiaolin, Ryadun Alexey A, Pavlov Dmitry I, Guselnikova Tatiana Y, Potapov Andrei S, Fedin Vladimir P
Department of Natural Sciences, Novosibirsk State University, 2 Pirogov Str., 630090, Novosibirsk, Russia.
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentiev Ave., 630090, Novosibirsk, Russia.
Angew Chem Int Ed Engl. 2023 Aug 28;62(35):e202306680. doi: 10.1002/anie.202306680. Epub 2023 Jul 19.
Solvothermal reaction of 5,5'-(pyridine-2,6-diylbis(oxy))diisophthalic acid (H L) with europium(III) or terbium(III) nitrates in acetonitrile-water (1 : 1) at 120 °C gave rise to isostructural 2D coordination polymers, [Ln(HL)(H O) ] (NIIC-1-Eu and NIIC-1-Tb), the layers of which are composed by eight-coordinated lanthanide(III) ions interconnected by triply deprotonated ligands HL . The layers are packed in the crystal without any specific intermolecular interactions between them, allowing the facile preparation of stable water suspensions, in which NIIC-1-Tb exhibited top-performing sensing properties through luminescence quenching effect with exceptionally low detection limits towards Fe (LOD 8.62 nM), ofloxacin (OFX) antibiotic (LOD 3.91 nM) and cotton phytotoxicant gossypol (LOD 2.27 nM). In addition to low detection limit and high selectivity, NIIC-1-Tb features fast sensing response (within 60-90 seconds), making it superior to other MOF-based sensors for metal cations and organic toxicants. The photoluminescence quantum yield of NIIC-1-Tb was 93 %, one of the highest among lanthanide MOFs. Mixed-metal coordination polymers NIIC-1-Eu Tb demonstrated efficient photoluminescence, the color of which could be modulated by the excitation wavelength and time delay for emission monitoring (within 1 millisecond). Furthermore, an original 2D QR-coding scheme was designed for anti-counterfeiting labeling of goods based on unique and tunable emission spectra of NIIC-1-Ln coordination polymers.
5,5'-(吡啶-2,6-二基双(氧基))二间苯二甲酸(H₂L)与铕(III)或铽(III)硝酸盐在乙腈-水(1∶1)混合溶剂中于120℃进行溶剂热反应，生成了同构的二维配位聚合物[Ln(HL)(H₂O)₃]（NIIC-1-Eu和NIIC-1-Tb），其层状结构由八配位的镧系(III)离子通过三重去质子化的配体H₂L相互连接而成。这些层状结构在晶体中堆积时，层与层之间没有任何特定的分子间相互作用，这使得能够轻松制备稳定的水悬浮液。在该水悬浮液中，NIIC-1-Tb通过发光猝灭效应表现出优异的传感性能，对铁(检测限8.62 nM)、氧氟沙星(OFX)抗生素(检测限3.91 nM)和棉花植物毒素棉酚(检测限2.27 nM)具有极低的检测限。除了低检测限和高选择性外，NIIC-1-Tb还具有快速的传感响应(60 - 90秒内)，使其优于其他用于金属阳离子和有机毒物检测的基于金属有机框架(MOF)的传感器。NIIC-1-Tb的光致发光量子产率为93%，是镧系MOF中最高的之一。混合金属配位聚合物NIIC-1-EuₓTb₁₋ₓ表现出高效的光致发光，其颜色可通过激发波长和发射监测的时间延迟(1毫秒内)进行调节。此外，基于NIIC-1-Ln配位聚合物独特且可调的发射光谱，设计了一种用于商品防伪标签的原创二维二维码编码方案。
