基于氮杂环配体的配位聚合物的合成、结构及性能研究
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摘要
本论文选择两类含氮有机配体与金属离子自组装,得到了八个新的金属-有机配位化合物。在结构及性能研究的基础上,考察配合物的几何构型、主配体和辅助配体对金属-有机配位化合物结构的影响,探究分子自组装原理。这些研究结果主要包括以下两个方面：
1、苯并三氮唑构筑的配合物。苯并三氮唑是很好的含氮类杂环配体,本文以苯并三氮唑为主配体与d10金属离子Hg(Ⅱ)和Zn(Ⅱ)自组装合成了两个结构新颖的五核簇合物：[NH2Me2][NaHg4(Btz)6I4] (Ⅰ1)、[Zn5(Btz)6(L)3(Ac)] (Ⅰ2) (HBtz=苯并三氮唑,HL=对氨基苯甲酸,HAc=醋酸)。配合物Ⅰ1属于四方晶系,Ⅰ4空间群,其中质子化的DMF没有参与配位,只是作为抗衡离子；I2中引入了对氨基苯甲酸等辅助配体,属于三斜晶系,P1空间群。在两个配合物中,配体HBtz采取μ3的配位模式,三个氮原子都参与配位,其中N1和N3桥联顶点的四个金属离子,并且这四个金属离子构成一个四面体结构,再通过6个HBtz的N2原子与中心金属离子配位,从而形成[M5(HBtz)6]五核金属簇合物。不同的是配合物Ⅰ1属于异核簇阴离子,配合物I2属于中性的同核簇合物。对配合物Ⅱ和Ⅱ2在空气气氛下的热稳定性能进行了测试分析。在室温下它们表现出了很好的荧光性能。
2、3-吡啶-4-苯甲酸构筑的配合物。3-吡啶-4-苯甲酸是很好的含氮杂环类吡啶羧酸配体,本文以它为构件分别与Pb(NO3)2、Cu(NO3)2、Sm(NO3)3、Gd(NO3)3、MnCO3和Zn(NO3)2在水热法和溶剂热的条件下反应,合成了六个新配位化合物：[Pb(pbc)2]n (Ⅱ1)、[Cu(pbc)2]n (Ⅱ2) [Sm(pbc)3(H2O)2]n·nH2O (Ⅱ3)、[Gd(pbc)3(H2O)2]n·nH2O (Ⅱ4)、Mn(pbc)2(H2O)4 (Ⅱ5)和[Zn(pbc)2(DMF)]n (Ⅱ6) (Hpbc＝3-吡啶-4-苯甲酸)。在这六个配合物中,配体表现出了五种不同的配位模式。配合物Ⅲ属于单斜晶系,C2手性空间群,一个C2轴贯通并平分Pb(Ⅱ)的八面体配位环境。配体pbc采用μ2-kO,O':kN模式桥联Pb(Ⅱ)形成具有(4,4)拓扑的二维聚合物结构,两个(4,4)网格相互穿插。配合物Ⅱ2属于三斜晶系,P1空间群,配体pbc采用cis-μ-kO:kN模式桥联金属离子,形成具有(4,4)拓扑结构的二重穿插的二维配位聚合物。配合物Ⅱ3和Ⅱ4同晶异质,属于三斜晶系P1空间群,配体pbc中COO-有两种配位模式：桥联配位(μ-kO:kO')和螯合配位模式。通过配体Hpbc的COO-的桥联作用将金属离子连接成了一个一维的链结构。配合物Ⅱ5属于单斜晶系,C2/c空间群,去质子的羧基没有参与配位,只有端基氮与金属离子连接,并通过π-π堆积以及复杂的氢键将单核配合物连接成一个二维的超分子结构。配合物Ⅱ6属于四方晶系,P41212手性空间群,配体的配位模式同Ⅱ1,通过配体的桥联作用将金属离子连接成一个具有(4,4)拓扑的二维网状结构。配合物Ⅱ1、Ⅱ2、Ⅱ3和Ⅱ5在空气气氛下的热稳定性能进行了测试分析。配合物Ⅱ4在室温下表现出了很好的荧光性能。并对配合物Ⅱ1、Ⅱ4和Ⅱ5的电化学性能进行了分析,在金属离子的微扰下,配体的电化学性质都发生了变化。
In this paper, two different N-containing ligands were chosen by us to assemble with metal ions, and as a result eight coordination compounds were obtained. Based on structure analyses and property investigation, the effect of the coordination geometry of metal ions, main ligands and accessorial ligands upon the structures of the resulting metal-organic complexes was studied, and the relative self-assembly principles were also explored. The main results are concluded as the following:
1. Complexes of HBtz (benzotriazole). Benzotriazole is a kind of good heterocyclic organic compounds containing N atom. Two new discrete Btz—bridged pentanuclear metal cluster complexes [NH2Me2][NaHg4(Btz)6I4] (Ⅰ1) and [Zn5(Btz)6(L)3(Ac)] (Ⅰ2) (Btz= deprotonated benzotriazole, L=ρ-aminobenzoate and Ac=aceticate) were synthesized. These two complexes use the HBtz as main ligand to self-assemble with Hg(Ⅱ) and Zn(Ⅱ). ComplexⅠ1 belongs to a tetragonal space groupⅠ4. Protonated dimethylamine is not coordinated but acts as a cation. ComplexⅠ2 withρ-aminobenzoate as accessorial ligand belongs to a triclinic space group P1.In both complexes HBtz ligand uses the three N atoms to coordinate with metal ions and acts as aμ3 bridge. In both complexes each apical metal ionb in the distored tetrahedron is bridged by N(1) and N(3), and N(2) atoms from six HBtz are ligated to the central metal ion, and finally, a pentanuclear [M5(HBtz)6] structure unit is formed. ComplexⅠ1 is a hetero-metal cluster whereas complexⅠ2 is a homo-metal cluster. The thermal properties of both complexes have been determined. Meanwhile, the pentanuclear metal cluster complexes both display strong blue fluorescent emission at room temperature.
2. Complexes of ligand Hpbc (3-pyride-4-yl-benzoic acid).3-Pyride-4-yl-benzoic acid is a kind of good rigid N-heterocyclic aromatic carboxylic acids. In this paper, we use this ligand to self-assemble with Pb(NO3)2, Cu(NO3)2, Sm(NO3)3, Gd(NO3)3, MnCO3 and Zn(NO3)2, respectively. The resulting six new complexes formulate [Pb(pbc)2]n (Ⅱ1), [Cu(pbc)2]n (Ⅱ2), [Sm(pbc)3(H2O)2]n·nH2O (Ⅱ3) [Gd(pbc)3(H2O)2]n·nH2 (Ⅱ4), Mn(pbc)2(H2O)4 (Ⅱ5) and [Zn(pbc)2(DMF)]n (Ⅱ6). ComplexⅡ1 belongs to monoclinic chiral space group C2. A C2 axis divides the octahedral coordination geometry of metal Pb(Ⅱ). Two Pb(Ⅱ) centers are bridged by ligand Hpbc in aμ2-kO,O':kN coordinated mode and form a two-fold interpenetrated metal-organic 2-D framework of (4,4) topology. ComplexⅡ2 belongs to triclinic space group P1. Two Cu(Ⅱ) centers are bridged by ligand Hpbc in a cis-μ-kO:kN coordinated mode and form a two-fold interpenetrated inorganic-organic 2-D framework of (4,4) topology, being very similar to that ofⅡ1. ComplexⅡ3 andⅡ4 belong to triclinic space group P1, and they are consistency in crystalline form and exhibit similar coordination environment and structure. In these two complexes, carboxyl groups COO- adopt two coordination patterns:bridging and chelating modes. Through the bridging COO-, earth-rare metal ions are linked into a 1-D chain structure. ComplexⅡ5 belongs to a monoclinic space group C2/c. In complexⅡ5, the ligands Hpbc act as terminal ligands to coordinate with metal ions through the nitrogen of pyridine, and the deprotonated carboxyl is not coordinated with metal ions. This mononuclear complex is threaded into a 2-D supermolecule structure by the effects ofπ…πstacking interactions and complicated hydrogen bonds. Complex 116 belongs to a tetragonal chiral space group P41212. The Zn(Ⅱ) centures are bridged by ligands Hpbc and form a 2-D metal-organic framework with (4,4) topology being very similar with the structure ofⅡ1, but there is no interpenetration. The thermal properties of complexesⅡ1,Ⅱ2,Ⅱ3 andⅡ5 have been determined and analysized. Complex 114 displays strong blue fluorescent emission at room temperature. The electrochemical properties of complexesⅡI,Ⅱ4 andⅡ5 were investigated too.
1、苯并三氮唑构筑的配合物。苯并三氮唑是很好的含氮类杂环配体,本文以苯并三氮唑为主配体与d10金属离子Hg(Ⅱ)和Zn(Ⅱ)自组装合成了两个结构新颖的五核簇合物：[NH2Me2][NaHg4(Btz)6I4] (Ⅰ1)、[Zn5(Btz)6(L)3(Ac)] (Ⅰ2) (HBtz=苯并三氮唑,HL=对氨基苯甲酸,HAc=醋酸)。配合物Ⅰ1属于四方晶系,Ⅰ4空间群,其中质子化的DMF没有参与配位,只是作为抗衡离子；I2中引入了对氨基苯甲酸等辅助配体,属于三斜晶系,P1空间群。在两个配合物中,配体HBtz采取μ3的配位模式,三个氮原子都参与配位,其中N1和N3桥联顶点的四个金属离子,并且这四个金属离子构成一个四面体结构,再通过6个HBtz的N2原子与中心金属离子配位,从而形成[M5(HBtz)6]五核金属簇合物。不同的是配合物Ⅰ1属于异核簇阴离子,配合物I2属于中性的同核簇合物。对配合物Ⅱ和Ⅱ2在空气气氛下的热稳定性能进行了测试分析。在室温下它们表现出了很好的荧光性能。
2、3-吡啶-4-苯甲酸构筑的配合物。3-吡啶-4-苯甲酸是很好的含氮杂环类吡啶羧酸配体,本文以它为构件分别与Pb(NO3)2、Cu(NO3)2、Sm(NO3)3、Gd(NO3)3、MnCO3和Zn(NO3)2在水热法和溶剂热的条件下反应,合成了六个新配位化合物：[Pb(pbc)2]n (Ⅱ1)、[Cu(pbc)2]n (Ⅱ2) [Sm(pbc)3(H2O)2]n·nH2O (Ⅱ3)、[Gd(pbc)3(H2O)2]n·nH2O (Ⅱ4)、Mn(pbc)2(H2O)4 (Ⅱ5)和[Zn(pbc)2(DMF)]n (Ⅱ6) (Hpbc＝3-吡啶-4-苯甲酸)。在这六个配合物中,配体表现出了五种不同的配位模式。配合物Ⅲ属于单斜晶系,C2手性空间群,一个C2轴贯通并平分Pb(Ⅱ)的八面体配位环境。配体pbc采用μ2-kO,O':kN模式桥联Pb(Ⅱ)形成具有(4,4)拓扑的二维聚合物结构,两个(4,4)网格相互穿插。配合物Ⅱ2属于三斜晶系,P1空间群,配体pbc采用cis-μ-kO:kN模式桥联金属离子,形成具有(4,4)拓扑结构的二重穿插的二维配位聚合物。配合物Ⅱ3和Ⅱ4同晶异质,属于三斜晶系P1空间群,配体pbc中COO-有两种配位模式：桥联配位(μ-kO:kO')和螯合配位模式。通过配体Hpbc的COO-的桥联作用将金属离子连接成了一个一维的链结构。配合物Ⅱ5属于单斜晶系,C2/c空间群,去质子的羧基没有参与配位,只有端基氮与金属离子连接,并通过π-π堆积以及复杂的氢键将单核配合物连接成一个二维的超分子结构。配合物Ⅱ6属于四方晶系,P41212手性空间群,配体的配位模式同Ⅱ1,通过配体的桥联作用将金属离子连接成一个具有(4,4)拓扑的二维网状结构。配合物Ⅱ1、Ⅱ2、Ⅱ3和Ⅱ5在空气气氛下的热稳定性能进行了测试分析。配合物Ⅱ4在室温下表现出了很好的荧光性能。并对配合物Ⅱ1、Ⅱ4和Ⅱ5的电化学性能进行了分析,在金属离子的微扰下,配体的电化学性质都发生了变化。
In this paper, two different N-containing ligands were chosen by us to assemble with metal ions, and as a result eight coordination compounds were obtained. Based on structure analyses and property investigation, the effect of the coordination geometry of metal ions, main ligands and accessorial ligands upon the structures of the resulting metal-organic complexes was studied, and the relative self-assembly principles were also explored. The main results are concluded as the following:
1. Complexes of HBtz (benzotriazole). Benzotriazole is a kind of good heterocyclic organic compounds containing N atom. Two new discrete Btz—bridged pentanuclear metal cluster complexes [NH2Me2][NaHg4(Btz)6I4] (Ⅰ1) and [Zn5(Btz)6(L)3(Ac)] (Ⅰ2) (Btz= deprotonated benzotriazole, L=ρ-aminobenzoate and Ac=aceticate) were synthesized. These two complexes use the HBtz as main ligand to self-assemble with Hg(Ⅱ) and Zn(Ⅱ). ComplexⅠ1 belongs to a tetragonal space groupⅠ4. Protonated dimethylamine is not coordinated but acts as a cation. ComplexⅠ2 withρ-aminobenzoate as accessorial ligand belongs to a triclinic space group P1.In both complexes HBtz ligand uses the three N atoms to coordinate with metal ions and acts as aμ3 bridge. In both complexes each apical metal ionb in the distored tetrahedron is bridged by N(1) and N(3), and N(2) atoms from six HBtz are ligated to the central metal ion, and finally, a pentanuclear [M5(HBtz)6] structure unit is formed. ComplexⅠ1 is a hetero-metal cluster whereas complexⅠ2 is a homo-metal cluster. The thermal properties of both complexes have been determined. Meanwhile, the pentanuclear metal cluster complexes both display strong blue fluorescent emission at room temperature.
2. Complexes of ligand Hpbc (3-pyride-4-yl-benzoic acid).3-Pyride-4-yl-benzoic acid is a kind of good rigid N-heterocyclic aromatic carboxylic acids. In this paper, we use this ligand to self-assemble with Pb(NO3)2, Cu(NO3)2, Sm(NO3)3, Gd(NO3)3, MnCO3 and Zn(NO3)2, respectively. The resulting six new complexes formulate [Pb(pbc)2]n (Ⅱ1), [Cu(pbc)2]n (Ⅱ2), [Sm(pbc)3(H2O)2]n·nH2O (Ⅱ3) [Gd(pbc)3(H2O)2]n·nH2 (Ⅱ4), Mn(pbc)2(H2O)4 (Ⅱ5) and [Zn(pbc)2(DMF)]n (Ⅱ6). ComplexⅡ1 belongs to monoclinic chiral space group C2. A C2 axis divides the octahedral coordination geometry of metal Pb(Ⅱ). Two Pb(Ⅱ) centers are bridged by ligand Hpbc in aμ2-kO,O':kN coordinated mode and form a two-fold interpenetrated metal-organic 2-D framework of (4,4) topology. ComplexⅡ2 belongs to triclinic space group P1. Two Cu(Ⅱ) centers are bridged by ligand Hpbc in a cis-μ-kO:kN coordinated mode and form a two-fold interpenetrated inorganic-organic 2-D framework of (4,4) topology, being very similar to that ofⅡ1. ComplexⅡ3 andⅡ4 belong to triclinic space group P1, and they are consistency in crystalline form and exhibit similar coordination environment and structure. In these two complexes, carboxyl groups COO- adopt two coordination patterns:bridging and chelating modes. Through the bridging COO-, earth-rare metal ions are linked into a 1-D chain structure. ComplexⅡ5 belongs to a monoclinic space group C2/c. In complexⅡ5, the ligands Hpbc act as terminal ligands to coordinate with metal ions through the nitrogen of pyridine, and the deprotonated carboxyl is not coordinated with metal ions. This mononuclear complex is threaded into a 2-D supermolecule structure by the effects ofπ…πstacking interactions and complicated hydrogen bonds. Complex 116 belongs to a tetragonal chiral space group P41212. The Zn(Ⅱ) centures are bridged by ligands Hpbc and form a 2-D metal-organic framework with (4,4) topology being very similar with the structure ofⅡ1, but there is no interpenetration. The thermal properties of complexesⅡ1,Ⅱ2,Ⅱ3 andⅡ5 have been determined and analysized. Complex 114 displays strong blue fluorescent emission at room temperature. The electrochemical properties of complexesⅡI,Ⅱ4 andⅡ5 were investigated too.
引文
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[1]J.H. Luo, Y.S. Zhao, H.W. Xu, et al. A Novel Helical Double-Layered Cobalt(Ⅱ)-Organic Framework with Tetranuclear [Co4(μ3-OH)2] Clusters Linked by an Unsymmetrical Pyridyl benzoate Ligand. Inorg. Chem.2007,46:9021-9023.
[2]Y.H. Zhao, H.B. Xu, K.Z. Shao, et al. Syntheses, characterization, and luminescent properties of three 3D lead-organic frameworks with 1D channels. Cryst. Growth. Des.2007,7,513.
[3]T.B. Lu, R.L. Luck. Five novel transition metal coordination polymers with 2D/3D framework structure based on flexible H2tzda and ancillary ligand bpe. Inorg. Chim. Acta.2003,351,345.
[4]Parbati Sengupta, Saktiprosad Ghosh, Thomas C. W. Mak. A new route for the synthesis of bis (pyridine dicarboxylato) bis (triphenylphosphine) complexes of ruthenium(Ⅱ) and X-ray structural characterization of the biologically active trans-[Ru(PPh3)2(L1H)2] (L1H2=pyridine 2,3-dicarboxylic acid). Polyhedron.2001,20:975-980.
[5](a) F. G. A New 4-Connected Co(Ⅱ) Coordination Framework With an Uncommon Two-Fold Interpenetrating Net:Synthesis, Structure and Luminescence Property. J Inorg Organomet Polym 2009,19:406-409. (b) Farouk Jaber,Francois Charbonnier, Rene Faure, Preparation and Crystal Struture of Tetraaqua-bis(hydrogenopyridine-2,3-dicarboxylate) bis (pyridine-2,3-dicarboxylate) hexa silver(Ⅰ) [Age(C7H4NO4)2(C7H3NO4)2(H2O)4]n. Polyhedron.1996,15(17):2929-2913.
[6]G.M. Sheldrick. SHELX-97, Program for the Solution and Refinement of Crystal Structures. University of Gottingen, Germany 1997.
[7]K. Nakamoto. Infrared and Raman spectra of inorganic and coordination compound. Wiley & Sons, New York,1986.