4，5-二氮芴-9-酮衍生物及配位聚合物的合成、结构与性质研究
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摘要
金属-有机配位聚合物作为一种新型的分子功能材料,凭借其独特的结构可剪裁性、多样的拓扑结构和在离子交换、吸附、分子识别、催化以及光、电、磁、手性拆分等领域的巨大潜在应用,受到各界科学家越来越多的关注。按照晶体工程的原理,通过选择特定几何构型的中心金属原子和特殊的有机配体可以在一定程度上实现晶体材料的定向设计与合成;同时,还可以通过选择功能性的中心金属离子和具有功能官能团的有机配体赋予目标配位聚合物以光、电、磁、手性拆分和催化等功能。由含氮螯合配体邻菲罗啉(phen)、4,5-二氮杂芴-9-酮(Dafo)合成配位聚合物的工作已有大量报道,然而合成具有新型结构的含氮配体仍然具有十分重要的意义,有广阔的发展空间和应用前景。通过对合成新型含氮配体和对已有含氮配体进行修饰,同时引入适合的第二羧酸配体,可以预期得到一些具有特殊性质的新型功能材料。Rao、Kitagawa 、Yaghi 等在这方面做了出色的工作,其中一个重要的合成策略是通过不同尺度,不同形状的芳香羧酸类配体与含氮的中性配体合成功能性多孔材料配位聚合物和具有互穿结构的配位聚合物。
本文中,我们合成了三种新的含氮多齿配体:4,5-二氮芴-9-肟(L1)、2-(4,5-二氮芴-9-亚胺基)苯酚(L2)、4-(4,5-二氮芴-9-亚胺基)苯甲酸(L3)。从分子设计的角度出发,同过选择对苯二甲酸和均苯四酸为第二配体,与过渡金属Zn(II)在不同的条件下形成了两种配合物:
以L1为第一配体,对苯二甲酸为第二配体与Zn(II)合成了一个具有新颖结构的三维配位聚合物[Zn_2(L1) (tp)_(1.5)(OH)](H_2O) 1。值得注意的是,结构中的μ3-O和金属离子Zn(II)构筑成类似于环己烷椅式构象的构筑单元Zn_4O_2(SBU),通过与对苯二甲酸桥联构成简单立方体结构。从拓扑学角度分析,该结构具有6节点的三维互穿网络结构。
同时,以L1为第一配体,均苯四酸为第二配体与Zn(II)合成了另一个具有新颖结构的三维配位聚合物 [Zn_2(L1) (btec)_(0.5)(OH)_2]2。在2中μ2-O的出现导致配合物维数升高,由μ2-O和Zn(II)构筑而成的具有八元环结构的Zn_4O_4构筑单元,与四个羧酸连接形成三维网络结构。在c轴方向,略去配体分子L1,得到孔径为(10.8A×8.15 A)的一维孔道。
氨基酸类配体因其具有较多的配位点,以及在生物等领域具有广泛的应用而倍受重视。我们以对乙酰氨基苯甲酸为配体,与过渡金属 Zn(II),Cd (II)反应得到了两个通过超分子作用形成的三维配合物 [Cd(CH_3CONHC_6H_4COO)_2·4(H_2O)]·2(H_2O) 3 和 [Zn(CH_3CONHC_6H_4COO)_2·4(H_2O)]·2(H_2O) 4。X 射线单晶衍射表明,在化合物中存在着多种氢键,使配合物构成了无限延伸的超分子三维网络结构。探讨了氢键在结构构建中所起的作用,并对化合物的光谱性质进行了研究。
Metal-organic coordination polymers-a new kind of functional molecule materials- have attracted much more attentions for their flexible tailoring, various topologies and promising application in ion-exchange, adsorption, molecular recognization, catalysts along with optics, electrics, magnetism and enantioslective separation. According to the principle of crystal engineering, it is possible that rational design and synthesis of porous crystalline materials by selecting certain geometric metal ions and special organic ligands; At the same time, coordination polymers can be endowed with optics, electric, magnetism, enantioselective separation and catalysis by selecting functional metal ions and organic ligands with functional groups. To today, there have been a lot of reports on coordination polymers, which generally constructed from various N-containing chelating bidentate ligand such as phen and Dafo. It is also important to synthesize the novel structure N-containing ligands which have widely developing space and potential application. Through modifying or synthesis the novel N-containing ligands and selecting suitable secondary multi-carboxylic ligands, a series of novel funditional materials with a range of special optics, electrics, magnetism properties can be designed and synthesized. In this filed, it is noteworthy that many hybrid compounds have been gotten by C. N. R. Rao, Kitagawa, Yaghi. A strategy based on selecting different size, different shape aromatic carboxylic and neutral N-containing ligands has been applied for the design and synthesis of new functional coordination polymers of porous and interpenetrating coordination polymers.
Here, Three new polypyridine ligands of 4,5-diazafluorene-9-one oxime(L1), 2-(4,5-Diazafluoren-9-ylideneamino)phenol(L2) and 4-(4,5-Diazafluoren-9-ylideneamino) benzoic acid(L3) have been successfully synthesized. From the viewpoint of molecular design, two rigid polycarboxyl ligands have been introduced into the complexes as the secondary ligands. A novel Three-Dimensional coordinaton polymer[Zn_2(L1) (tp)_(1.5)(OH)](H_2O) 1 has been constructed with L1 in the presence of an additional terephthalate. It is noteworthy that the structure consisits of interpenetrating six-connected topology nets. In its most symmetrical form this net consists of nodes with a chair form(Zn4O_2)building of μ3-O bridge and Zn(II) and has a primitive cubic unit cell building of terephthalate. At the same time another three-dimensional coordination coordination polymer[Zn_2(L1)(btec)_(0.5)(OH)_2] 2 have been obtained bridging in 1,2,4,5-benzenete- tracarboxylate. The presence of μ2-O bridge result in the increment of the dimension of polymers. Tortile octagonal Zn_4O_4 building of μ2-O is edge-bridged by four carboxylates to give a novel topology structure. Viewed along the c zxis, there are channels(10.8A×8.15A)
in the structure filled by L1 ligands. Amino acid is a kind of well-exploited ligand and it has more coordinated sites, so it is of great interest in biochemisty and other fields. Here a flexible ligand 4-acetamidobenzic acid was used for ligand to form complex.Two 3-dimensional suparmolecular coordination polymer [Cd(CH_3CONHC_6H_4COO)_2·4(H_2O)]·2(H_2O) 3 and [Zn(CH_3CONHC_6H_4 COO)_2·4(H_2O)]·2(H_2O) 4 have been got in the condition of existing of the transition metal Zn(II) and Cd(II). The crystal structure of the compound was determined by X-ray diffraction. The result shows that the crystal possesses three 3-dimensional infinite network structure constructed by many kinds hydrogen bond, forming the supramolecule. The various kinds of hydrogen bond in the compound and their effect on the crystal structure are discussed. At last the spectra studies are here.
本文中,我们合成了三种新的含氮多齿配体:4,5-二氮芴-9-肟(L1)、2-(4,5-二氮芴-9-亚胺基)苯酚(L2)、4-(4,5-二氮芴-9-亚胺基)苯甲酸(L3)。从分子设计的角度出发,同过选择对苯二甲酸和均苯四酸为第二配体,与过渡金属Zn(II)在不同的条件下形成了两种配合物:
以L1为第一配体,对苯二甲酸为第二配体与Zn(II)合成了一个具有新颖结构的三维配位聚合物[Zn_2(L1) (tp)_(1.5)(OH)](H_2O) 1。值得注意的是,结构中的μ3-O和金属离子Zn(II)构筑成类似于环己烷椅式构象的构筑单元Zn_4O_2(SBU),通过与对苯二甲酸桥联构成简单立方体结构。从拓扑学角度分析,该结构具有6节点的三维互穿网络结构。
同时,以L1为第一配体,均苯四酸为第二配体与Zn(II)合成了另一个具有新颖结构的三维配位聚合物 [Zn_2(L1) (btec)_(0.5)(OH)_2]2。在2中μ2-O的出现导致配合物维数升高,由μ2-O和Zn(II)构筑而成的具有八元环结构的Zn_4O_4构筑单元,与四个羧酸连接形成三维网络结构。在c轴方向,略去配体分子L1,得到孔径为(10.8A×8.15 A)的一维孔道。
氨基酸类配体因其具有较多的配位点,以及在生物等领域具有广泛的应用而倍受重视。我们以对乙酰氨基苯甲酸为配体,与过渡金属 Zn(II),Cd (II)反应得到了两个通过超分子作用形成的三维配合物 [Cd(CH_3CONHC_6H_4COO)_2·4(H_2O)]·2(H_2O) 3 和 [Zn(CH_3CONHC_6H_4COO)_2·4(H_2O)]·2(H_2O) 4。X 射线单晶衍射表明,在化合物中存在着多种氢键,使配合物构成了无限延伸的超分子三维网络结构。探讨了氢键在结构构建中所起的作用,并对化合物的光谱性质进行了研究。
Metal-organic coordination polymers-a new kind of functional molecule materials- have attracted much more attentions for their flexible tailoring, various topologies and promising application in ion-exchange, adsorption, molecular recognization, catalysts along with optics, electrics, magnetism and enantioslective separation. According to the principle of crystal engineering, it is possible that rational design and synthesis of porous crystalline materials by selecting certain geometric metal ions and special organic ligands; At the same time, coordination polymers can be endowed with optics, electric, magnetism, enantioselective separation and catalysis by selecting functional metal ions and organic ligands with functional groups. To today, there have been a lot of reports on coordination polymers, which generally constructed from various N-containing chelating bidentate ligand such as phen and Dafo. It is also important to synthesize the novel structure N-containing ligands which have widely developing space and potential application. Through modifying or synthesis the novel N-containing ligands and selecting suitable secondary multi-carboxylic ligands, a series of novel funditional materials with a range of special optics, electrics, magnetism properties can be designed and synthesized. In this filed, it is noteworthy that many hybrid compounds have been gotten by C. N. R. Rao, Kitagawa, Yaghi. A strategy based on selecting different size, different shape aromatic carboxylic and neutral N-containing ligands has been applied for the design and synthesis of new functional coordination polymers of porous and interpenetrating coordination polymers.
Here, Three new polypyridine ligands of 4,5-diazafluorene-9-one oxime(L1), 2-(4,5-Diazafluoren-9-ylideneamino)phenol(L2) and 4-(4,5-Diazafluoren-9-ylideneamino) benzoic acid(L3) have been successfully synthesized. From the viewpoint of molecular design, two rigid polycarboxyl ligands have been introduced into the complexes as the secondary ligands. A novel Three-Dimensional coordinaton polymer[Zn_2(L1) (tp)_(1.5)(OH)](H_2O) 1 has been constructed with L1 in the presence of an additional terephthalate. It is noteworthy that the structure consisits of interpenetrating six-connected topology nets. In its most symmetrical form this net consists of nodes with a chair form(Zn4O_2)building of μ3-O bridge and Zn(II) and has a primitive cubic unit cell building of terephthalate. At the same time another three-dimensional coordination coordination polymer[Zn_2(L1)(btec)_(0.5)(OH)_2] 2 have been obtained bridging in 1,2,4,5-benzenete- tracarboxylate. The presence of μ2-O bridge result in the increment of the dimension of polymers. Tortile octagonal Zn_4O_4 building of μ2-O is edge-bridged by four carboxylates to give a novel topology structure. Viewed along the c zxis, there are channels(10.8A×8.15A)
in the structure filled by L1 ligands. Amino acid is a kind of well-exploited ligand and it has more coordinated sites, so it is of great interest in biochemisty and other fields. Here a flexible ligand 4-acetamidobenzic acid was used for ligand to form complex.Two 3-dimensional suparmolecular coordination polymer [Cd(CH_3CONHC_6H_4COO)_2·4(H_2O)]·2(H_2O) 3 and [Zn(CH_3CONHC_6H_4 COO)_2·4(H_2O)]·2(H_2O) 4 have been got in the condition of existing of the transition metal Zn(II) and Cd(II). The crystal structure of the compound was determined by X-ray diffraction. The result shows that the crystal possesses three 3-dimensional infinite network structure constructed by many kinds hydrogen bond, forming the supramolecule. The various kinds of hydrogen bond in the compound and their effect on the crystal structure are discussed. At last the spectra studies are here.
引文
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