Zhou Yan, Hu Qin, Yu Fei, Ran Guang-Ying, Wang Hai-Ying, Shepherd Nicholas D, D'Alessandro Deanna M, Kurmoo Mohamedally, Zuo Jing-Lin
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, P. R. China.
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610066, P. R. China.
J Am Chem Soc. 2020 Nov 13. doi: 10.1021/jacs.0c09009.
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(CS(CHCOOH))], which can be considered as the inorganic analogue of the organic tetrathiafulvalene-tetrabenzoic acid (HTTFTB). Likewise, [Ni(CS(CHCOOH))] is a redox-active linker for new functional metal-organic frameworks, as demonstrated here with the synthesis of [Mn{Ni(CS(CHCOO))}(HO)]·2DMF, (, DMF = -dimethylformamide). is isomorphic to the reported [Mn(TTFTB)(HO)] () but is a better electrochemical glucose sensor due to the multiple oxidation-reduction states of the [NiS] core, which allow glucose to be oxidized to glucolactone by the high oxidation state [NiS] center. As a non-enzymatic glucose sensor, on Cu foam (), , was synthesized by a one-step hydrothermal method and exhibited an excellent electrochemical performance. The fabricated electrode offers a high sensitivity of 27.9 A M cm, with a wide linear detection range from 2.0 × 10 to 2.0 × 10 M, a low detection limit of 1.0 × 10 M (signal/noise = 3), and satisfactory stability and reproducibility.
用能够与金属配位的基团对氧化还原活性四硫富瓦烯（TTF）核进行功能化，为调控有机-无机杂化材料的结构和电子性质提供了新的视角。为了扩展这一概念，我们现已合成了双（二硫纶-二苯甲酸）镍，[Ni(CS(CHCOOH))]，它可被视为有机四硫富瓦烯-四苯甲酸（HTTFTB）的无机类似物。同样，[Ni(CS(CHCOOH))]是用于新型功能金属有机框架的氧化还原活性连接体，在此通过合成[Mn{Ni(CS(CHCOO))}(HO)]·2DMF（，DMF = N,N-二甲基甲酰胺）得以证明。它与已报道的[Mn(TTFTB)(HO)]（）同构，但由于[NiS]核的多个氧化还原态，使其成为更好的电化学葡萄糖传感器，这些氧化还原态能使葡萄糖被高氧化态的[NiS]中心氧化为葡萄糖酸内酯。作为一种非酶葡萄糖传感器，通过一步水热法在泡沫铜（）上合成了，，并表现出优异的电化学性能。所制备的电极具有27.9 A M cm的高灵敏度，线性检测范围宽，从2.0×10到2.0×10 M，检测限低至1.0×10 M（信噪比 = 3），且具有令人满意的稳定性和重现性。
