南京大学左景林团队研究了一种基于双镍二硫代烯的金属有机骨架结构的合成，晶体结构，及其作为电化学葡萄糖传感器的应用。 这一研究成果于2020年11月13日发表在国际顶尖学术期刊《美国化学会志》。

将氧化还原活性四硫富瓦烯(TTF)核与金属配位基团功能化，为有机-无机杂化材料的结构调控和电子性能提供了新的前景。

为了扩展这一概念，研究团队合成了双镍（二硫代烯二苯甲酸）[Ni(C2S2(C6H4COOH)2)2]，它可以被认为是有机四硫富瓦烯四苯甲酸（H4TFTB）的无机类似物。同样，[Ni(C2S2(C6H4COOH)2)2]是一种新型功能金属-有机框架的氧化还原活性连接剂，如该文通过[Mn2{Ni(C2S2(C6H4COO)2)2}(H2O)2]·2DMF， (1, DMF = N,N-二甲基甲酰胺)的合成所证实。1与报道的[Mn2(TTFTB)(H2O)2](2)同构，但由于[NiS4]核心的多重氧化-还原状态，使葡萄糖被高氧化态[NiS4]中心氧化为葡萄糖内酯，因此是一种更好的电化学葡萄糖传感器。

采用一步水热法合成了1-CF，作为一种非酶葡萄糖传感器，具有良好的电化学性能。制备的1-CF电极灵敏度为27.9A M^–1 cm^–2，线性检测范围从2.0×10^-6到2.0×10^-3M，检测下限为1.0×10^-7M（信噪比为3），稳定性和重现性令人满意。

附：英文原文

Title: A Metal–Organic Framework Based on a Nickel Bis(dithiolene) Connector: Synthesis, Crystal Structure, and Application as an Electrochemical Glucose Sensor

Author: Yan Zhou, Qin Hu, Fei Yu, Guang-Ying Ran, Hai-Ying Wang, Nicholas D. Shepherd, Deanna M. D’Alessandro, Mohamedally Kurmoo, Jing-Lin Zuo

Issue&Volume: November 13, 2020

Abstract: Functionalizing the redox-active tetrathiafulvalene (TTF) core with groups capable of coordination to metals provides new perspectives on the modulation of architectures and electronic properties of organic–inorganic hybrid materials. With a view to extending this concept, we have now synthesized nickel bis(dithiolene-dibenzoic acid), [Ni(C2S2(C6H4COOH)2)2], which can be considered as the inorganic analogue of the organic tetrathiafulvalene-tetrabenzoic acid (H4TTFTB). Likewise, [Ni(C2S2(C6H4COOH)2)2] is a redox-active linker for new functional metal–organic frameworks, as demonstrated here with the synthesis of [Mn2{Ni(C2S2(C6H4COO)2)2}(H2O)2]·2DMF, (1, DMF = N,N-dimethylformamide). 1 is isomorphic to the reported [Mn2(TTFTB)(H2O)2] (2) but is a better electrochemical glucose sensor due to the multiple oxidation–reduction states of the [NiS4] core, which allow glucose to be oxidized to glucolactone by the high oxidation state [NiS4] center. As a non-enzymatic glucose sensor, 1 on Cu foam (CF), 1-CF, was synthesized by a one-step hydrothermal method and exhibited an excellent electrochemical performance. The fabricated 1-CF electrode offers a high sensitivity of 27.9 A M^–1 cm^–2, with a wide linear detection range from 2.0 × 10^–6 to 2.0 × 10^–3 M, a low detection limit of 1.0 × 10^–7 M (signal/noise = 3), and satisfactory stability and reproducibility.

DOI: 10.1021/jacs.0c09009

Source: https://pubs.acs.org/doi/10.1021/jacs.0c09009