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以1,2,4,5-均苯四羧酸(btec)和二-吡啶-(3,2-d:2,3′-f)-二氮萘(Dpq)为混合配体,水热合成了一种三维超分子配合物:[Co2(Dpq)2(btec)(H2O)6].2H2O,并通过元素分析、红外光谱、热重分析和X射线衍射测试技术对其结构进行了表征。晶体结构解析结果表明,该配合物属单斜晶系,P21/c空间群,晶胞参数为:a=0.8978(5)nm,b=2.9822(16)nm,c=0.7058(4)nm,β=94.199(6)°,V=1.8848(18)nm3,Z=2,R1=0.0350,wR2=0.0796。该化合物由1,2,4,5-均苯四羧酸中羧基氧原子、二-吡啶-(3,2-d:2,3′-f)-二氮萘的螯合氮原子及水分子中氧原子与中心Co(Ⅱ)离子配位,形成六配位的扭曲八面体几何构型。羧酸作为桥连配体连接2个相邻的中心Co(Ⅱ)离子形成钴配合物的双核单元,双核单元之间通过氢键及π-π堆积作用相互连接构成三维超分子网状结构。电化学实验结果表明,钴配合物修饰碳糊电极(Co-CPE)在0.1mol/L乙酸-乙酸钠缓冲溶液中电位范围+600～-300mV内有1对归属于Co(Ⅱ)/Co(Ⅲ)的氧化还原峰,而且此修饰电极对亚硝酸根的氧化有很好的电催化效果。
Using 1,2,4,5-benzenetricarboxylic acid (btec) and di-pyridine (3,2-d: 2,3’-f) A three-dimensional supramolecular complex [Co2 (Dpq) 2 (btec) (H2O) 6] .2H2O was synthesized and its structure was characterized by elemental analysis, IR, TG and XRD . The crystal structure analysis results show that the complex belongs to the monoclinic space group P21 / c with a = 0.8978 (5) nm, b = 2.9822 (16) nm and c = 0.7058 β = 94.199 (6) °, V = 1.8848 (18) nm3, Z = 2, R1 = 0.0350, wR2 = 0.0796. The compound consists of a carboxyl oxygen atom in 1,2,4,5-benzenetetracarboxylic acid, a chelating nitrogen atom of di-pyridine- (3,2-d: 2,3’-f) -naphthyridine and a water The oxygen atom in the molecule coordinates with the central Co (Ⅱ) ion to form a hexacoordinated twisted octahedral geometry. Carboxylic acid acts as a bridging ligand to connect two adjacent central Co (Ⅱ) ions to form a dinuclear unit of a cobalt complex. The binuclear units are interconnected by hydrogen bonds and π-π stacking to form a three-dimensional supramolecular network structure. The results of electrochemical experiments showed that there was a pair of Co-CPE (Co-CPE) in the range of 600 ~ 300mV in 0.1mol / L acetic acid-sodium acetate buffer solution. Ⅲ) redox peaks, and the modified electrode oxidation of nitrite has a good electrocatalytic effect.