一个二维钴配位聚合物的合成、结构及光催化性质

doi:10.11944/j.issn.1000-0518.2015.03.140239

摘要/Abstract

摘要：

以N,N'-二(3-吡啶基)-吡啶-3,5-二甲酰胺(bppdca)和2-巯乙酸基烟酸(L)为混合配体,利用水热合成方法获得了一个二维的Co(Ⅱ)配位聚合物:{[Co(bppdca)(L)]·3H₂O}_n,并通过元素分析、IR和单晶X射线衍射等技术手段确定了其结构。该配合物分子式为C₂₅H₂₄N₆O₉SCo,单斜晶系,P2₁/c空间群,a=1.07419(9) nm,b=0.86166(6) nm,c=2.9853(2) nm,β=96.772(1)°,Z=4,V=2.743 9(4) nm³,M_r=643.49,D_c=1.558 g/cm³,F(000)=1324,μ=0.766 mm^-1,S=1.051,R=0.0406,wR=0.1160。晶体结构分析表明,配合物中的CoⅡ与来自2个bppdca配体的2个N原子、1个L阴离子的单齿羧基O原子和S原子以及来自另一个L阴离子的一个羧基中的2个O原子配位形成八面体配位构型。相邻的Co^Ⅱ通过L阴离子连接成一维螺旋链[Co(L)]_n,相邻的左、右螺旋链通过成对的bppdca配体拓展成二维配位网络。最终,相互平行的二维网络通过氢键作用拓展成三维超分子框架。另外,还研究了该化合物的热稳定性、电化学性质、荧光性质以及选择性光催化性质。CCDC: 1010786

关键词: 钴配位聚合物, 水热合成, 晶体结构, 光致发光性质, 选择性光催化性质

Abstract:

A new two-dimensional Co(Ⅱ) coordination polymer {[Co(bppdca)(L)] 3H₂O}_n[bppdca=N,N'-bis(pyridine-3-yl)pyridine-3,5-dicarboxamide, L=2-carboxymethylsulfanyl nicotinic acid] has been hydrothermally synthesized and structurally characterized by elementary analysis, IR and single crystal X-ray diffraction analysis. [Co(bppdca)(L)]·3H₂O is monoclinic with a space group of P2₁/c, a=1.07419(9) nm, b=0.86166(6) nm, c=2.9853(2) nm, β=96.772(1)°, Z=4, V=2.7439(4) nm³, M_r=643.49, D_c=1.558 g/cm³, F(000)=1324, μ=0.766 mm^-1, S=1.051, the final R=0.0406 and wR=0.1160. The crystal structure analysis indicates that the Co(Ⅱ) cation is six-coordinated by two nitrogen atoms from two bppdca ligands, one monodentate O atom and one S atom from one L anion, two chelating O atoms from another L anion. The adjacent Co(Ⅱ) ions are linked by L anions to form one-dimensional helical chain [Co(L)]_n and the chains are further connected by pairs of bppdca ligands to generate a two-dimensional network. Finally, the networks are linked by hydrogen bonding to form a three-dimensional supramolecular framework. Moreover, the thermal stability, electrochemical property, photoluminescence property and selective photocatalytic activity of the title compound are investigated. CCDC:1010786

Key words: Co(Ⅱ) coordination polymer, hydrothermal synthesis, crystal structure, photoluminescence property, selective photocatalytic properties

中图分类号:

刘国成, 陈乃丽, 王秀丽, 熊莹. 一个二维钴配位聚合物的合成、结构及光催化性质[J]. 应用化学, 2015, 32(3): 335-341.

LIU Guocheng, CHEN Naili, WANG Xiuli, XIONG Ying. Synthesis, Crystal Structure and Photocatalytic Properties of a Two-Dimensional Cobalt Coordination Polymer[J]. Chinese Journal of Applied Chemistry, 2015, 32(3): 335-341.

参考文献

[1]	Bi Y F,Wang X T,Liao W P,et al.A {Co32} Nanosphere Supported by p-tert-Butylthiacalix[4]arene[J]. J Am Chem Soc,2009,131(33):11650-11651.
[2]	Li J R,Sculley J,Zhou H C. Metal-Organic Frameworks for Separations[J]. Chem Rev,2012,112(2):869-932.
[3]	Cui Y J,Yue Y F,Qian G D,et al.Luminescent Functional Metal-Organic Frameworks[J]. Chem Rev,2012,112(3):1126-1162.
[4]	Inokuma Y,Kawano M,Fujita M. Crystalline Molecular Flasks[J]. Nat Chem,2011,3(5):349-358.
[5]	WANG Jianhui,GUO Liqin,RUAN Wenjuan,et al.Synthesis and Electrochemiscal Properties of Salen Type Copper(Ⅱ) and Nickel(Ⅱ) Complexes[J]. Chinese J Appl Chem,2014,31(3):303-309(in Chinese). 王建辉,郭莉芹,阮文娟,等. Salen型铜(Ⅱ)和镍(Ⅱ)配合物的合成与电化学性质[J]. 应用化学,2014,31(3):303-309.
[6]	Sun Y X,Sun W Y. Influence of Temperature on Metal-Organic Frameworks[J]. Chinese Chem Lett,2014,25(6):823-828.
[7]	Zhao X L,Sun W Y. The Organic Ligands with Mixed N-/O-donors Used in Construction of Functional Metal Organic Frameworks[J]. Cryst Eng Comm,2014,16(16):3247-3258.
[8]	LI Xinxiong,CHENG Lin,FANG Weihui,et al.A Series of Open-Frameworks Constructed from Polyoxoanion Clusters and Copper-tetrazolate Complexes:Synthesis, Structure and Properties[J]. Acta Chim Sin,2013,71(2):179-185(in Chinese). 李新雄,程琳,方伟慧,等. 基于金属氧簇和铜-四氮唑配合物构建的空旷骨架:合成、结构及性能[J]. 化学学报,2013,71(2):179-185.
[9]	NI Chunyan,CHEN Yang,LI Duanxiu,et al.Halide-Directed Synthesis of Coordination Polymers [Hg2X4(ppt)]n(X=I and Br, ppt=1-(4-Pyridyl)-pyridinium-4-thiolate) with Different One-Dimensional Chain Structures and Third-Order Nonlinear Optical Properties[J]. Acta Chim Sin,2013,71(6):906-912(in Chinese). 倪春燕,陈阳,李端秀,等. 卤离子导向合成配位聚合物[Hg2X4(ppt)]n(X=I和Br;ppt=1-(4-吡啶基)-吡啶铵-4-硫醇盐)及不同的一维链状结构和三阶非线性光学响应[J]. 化学学报,2013,71(6):906-912.
[10]	Wang X L,Luan J,Sui F F,et al.Structural Diversities and Fluorescent and Photocatalytic Properties of a Series of CuⅡ Coordination Polymers Constructed from Flexible Bis-pyridyl-bis-amide Ligands with Different Spacer Lengths and Different Aromatic Carboxylates[J]. Cryst Growth Des,2013,13(8):3561-3576.
[11]	Sun G M,Luo F,Song Y M,et al.A Self-catenated Network Containing Unprecedented 0D+2D→2D Polycatenation Array[J]. Dalton Trans,2012,41(38):11559-11561.
[12]	Zhao Y,Lv M F,Fan J,et al.Syntheses,Structures and Photoluminescence Properties of Cadmium(Ⅱ) and Zinc(Ⅱ) Complexes with Pyridinylcarboxamide-Containing Ligand[J]. Inorg Chim Acta,2011,377:138-143.
[13]	Mu Y J,Zhao Y F,Xu H,et al.Influence of Halide Anions on the Construction of Coordination Complexes with Mercury(Ⅱ) Center:Syntheses, Structures and Photoluminescent Properties[J]. J Mol Struct,2009,935:144-150.
[14]	Wang X L,Huang J J,Liu L L,et al.Assembly of Zn/Cd Coordination Polymers Containing Helixes or Polycatenane Structures Tuned by the Tripyridyl bis-amide Ligands with Different Spacer:Syntheses, Structures, Photoluminescent and Photocatalytic Properties[J]. Cryst Eng Comm,2013,15(10):1960-1969.
[15]	Wang X L,Huang J J,Liu L L,et al.pH-dependent Two Novel 3D Polynuclear Cobalt(Ⅱ) Cluster-based Metal-organic Frameworks Constructed from a Tri-pyridyl-bis-amide and a Polycarboxylate:Assembly, Structures and Properties[J]. RSC Adv,2013,3(33):13944-13952.
[16]	Wang X L,Chen N L,Liu G C,et al.Effect of Organic Dicarboxylates with Different Rigidity on the Construction of Cobalt(Ⅱ) Complexes with a Semi-rigid Tripyridyl-bis-amide Ligand[J]. Z Anorg Allg Chem,2014,640(2):476-482.
[17]	Mu Y J,Zhao Y F,Xu H,et al.Influence of Halide Anions on the Construction of Coordination Complexes with Mercury(Ⅱ) Center:Syntheses, Structures and Photoluminescent Properties[J]. J Mol Struct,2009,935(1-3):144-150.
[18]	Jiang X R,Wang X J, Feng Y L. Two New Nickel(Ⅱ) Complexes Constructed by 2-Carboxymethylsulfanyl Nicotinic Acid with Different N-containing Auxiliary Ligands[J]. Inorg Chim Acta,2012,383:8-45.
[19]	Sheldrick G M. SHELXS 97,Program for Crystal Structure Solution,G ttingen University,Germany,1997
[20]	Sheldrick G M. SHELXL 97,Program for Crystal Structure Refinement,G ttingen University,Germany,1997
[21]	LIN Hongyan,WANG Xiuli,LIU Guocheng. Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of 3D Supramolecular Compound [Co2(Dpq)2(btec)(H2O)6]·2H2O[J]. Chinese J Appl Chem,2009,26(10):1216-1221(in Chinese). 林宏艳,王秀丽,刘国成. 三维超分子配合物[Co2(Dpq)2(btec)(H2O)6]·2H2O的水热合成、晶体结构和电化学性质[J]. 应用化学,2009,26(10):1216-1221.
[22]	Winkler K,Plonska M E,Basa A,et al.Mediated Electrocatalysis at the Electrodes Covered with [MⅢ(bpy)3](ClO4)3(M=Co and Fe) in the Presence of Electroactive Solutes[J]. Electroanalysis,2003,15(1):55-64.
[23]	Shi X,Zhu G S,Fang Q R,et al.Novel Supramolecular Frameworks Self-Assembled from One-Dimensional Polymeric Coordination Chains[J]. Eur J Inorg Chem,2004,2004(1):185-191.
[24]	Amendola V,Fabbrizzi L,Foti F,et al.Light-emitting Molecular Devices Based on Transition Metals[J]. Coord Chem Rev,2006,250(3/4):273-299.
[25]	Wang X L,Luan J,Lin H Y,et al.The Design and Construction of a Aeries of Metal Organic Coordination Polymers Based on Two Isomeric Semi-Rigid Bis-pyridyl-bis-amide Ligands and Three Aromatic Polycarboxylates[J]. Cryst Eng Comm,2013,15(46):9995-10006.