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:[Co_2(Dpq)_2(btec)(H_2O)_6]·2H_2O, 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,P2_1/c 空间群,晶胞参数为:a=0.897 8(5) nm,b=2.982 2(16) nm,c=0.705 8(4) nm,β=94.199(6)°,V=1.884 8(18) nm~3,Z= 2,R_1=0.035 0,wR_2=0.079 6. 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0.1 mol/L乙酸-乙酸钠缓冲溶液中电位范围+600～-300 mV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.
A new 3D supramolecular compound, [Co_2(Dpq)_2(btec)(H_2O)_6]·2H_2O, was obtained from the hydrothermal reaction of cobalt(Ⅱ) nitrate with mixed ligands [1,2,4,5-benzenetetracarboxylate(btec) and dipyrido[3,2-d:2′,3′-f]quinoxaline(Dpq)], and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The results reveal that the compound belongs to the monoclinic system with P2_1/c space group. The cell parameters are a=0.897 8(5) nm, b=2.982 2(16) nm, c=0.705 8(4) nm, β=94.199(6)°, V=1.884 8(18) nm~3, Z=2, R_1=0.035 0, wR_2=0.079 6. The Co(Ⅱ) is coordinated with two nitrogen atoms of one Dpq molecule, one oxygen atom from the bridging ligand btec, and three oxygen atoms from coordinated water molecules, respectively, rendering a six-coordinate mode in a distorted octahedron geometry. Two adjaceut Co(Ⅱ) ions are linked by the bridging ligand btec to construct a dinuclear unit. The 3D supramolecular network of the title compound is formed through hydrogen bonds and π-π stacking interactions. Moreover, the electrochemical properties of carbon paste electrode modified by the compound(Co-CPE) were studied, and the results indicate that the Co-CPE exhibited one-electron redox wave in potential range of 600 to -300 mV due to the metal cobalt ion redox Co(Ⅱ)/Co(Ⅲ). The Co-CPE has good electrocatalytic activity toward the oxidation of nitrite in a 0.1 mol/L HAc-NaAc solution.
参考文献
| [1] | Barthelet K,Marrot J,Riou D.Angew Chem Int Ed[J],2002,41:281 |
| [2] | Bu X,Tong M,Chang H.Angew Chem Int Ed[J],2004,43:192 |
| [3] | GUO Ying-Chen(郭应臣),ZHUO Li-Hong(卓立宏),DUAN Yu-Fang(段玉芳),HUANG Qun-Zeng(黄群增).Chinese J Appl Chem(应用化学)[J],2007,24:318 |
| [4] | Wang X L,Bi Y F,Lin H Y,Liu G C,Chen B K.J Organome Chem[J],2007,692:4 353 |
| [5] | Wang X L,Zhao H Y,Lin H Y,Liu G C,Fang J N,Chen B K.Electroanalysis[J],2008,20:1 055 |
| [6] | Wang X L,Lin H Y,Liu G C,Zhao H Y,Chen B K.J Organome Chem[J],2008,693:2 767 |
| [7] | DONG Shao-Jun(董绍俊),CHE Guang-Li(车广礼),XIE Yuan-Wu(谢远武),Chief-Edr(主编).Chemical Modified Electrode(化学修饰电极)[M].BeiJing(北京):Science Press(科学出版社),2003:1 |
| [8] | Cheung K C,Wong W L,Ma D L,Lai T S,Wong K Y.Coord Chem Rev[J],2007,251:2 367 |
| [9] | Collins J G,Sleeman A D,Aldrich-Wright J R,Greguric I,Hambley T W.Inorg Chem[J],1998,37:3 133 |
| [10] | Sheldrick G M.SHELXS 97,Program for Crystal Structure Solution,G(o)ttingen University,Germany,1997 |
| [11] | Sheldrick G M.SHELXL 97,Program for Crystal Structure Refinement,G(o)ttingen University,Germany,1997 |
| [12] | Sun D F,Cao R,Liang Y C,Shi Q,Su W P,Hong M C.J Chem Soc,Dalton Trans[J],2001:2 335 |
| [13] | Winkler K,Plonska M E,Basa A,Lach M,Balch A L.Electroanalysis[J],2003,15:55 |
| [14] | Sener M K,Koca A,Gül A,Koak M B.Polyhedron[J],2007,26:1 070 |
| [15] | Chen S M.J Electroanal Chem[J],1998,457:23 |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%