含氮多齿配体构筑的配位聚合物的合成、结构及性质研究
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摘要
本论文利用1-(1H-1,2,4-三唑基甲基)-3,5-双吡啶基-1,2,4-三唑(简写为tmbpt)的几种异构体作为主配体,以过渡金属阳离子作为中心金属离子,与多元羧酸根阴离子或多金属氧酸盐阴离子在水热条件下自组装,构筑了一系列具有多种结构的化合物。探索这些化合物的合成条件,研究它们的网络所属拓扑类型,并考察含氮配体、阴离子和过渡金属的种类对化合物结构的影响,并探究这些化合物的结构和性质之间的关系。本文在水热条件下合成了26个配位聚合物,用红外光谱(IR)、元素分析和热重分析对这些化合物进行了表征。此外,还研究了这些化合物的发光性质及光催化行为。1.以含氮多齿配体1-(1H-1,2,4-三唑基甲基)-3,5-双(4-吡啶基)-1,2,4-三唑(简写为4,4'-tmbpt)作为主配体,芳香多元羧酸(o-H2bdc=1,2-benzenedicarboxylic acid、m-H2bdc=1,3-benzenedicarboxylic acid、5-OH-H2bdc=5-hydroxy-1,3-benzenedicarboxylic acid1,2,3-H3btc=1,2,3-benzenetricarboxylic acid和p-H2bdc=1,4-benzenedicarboxylic acid)作为辅助配体,选用Zn(Ⅱ)和Cd(Ⅱ)作为中心金属离子,合成了8个配位聚合物。化合物1、3和7展示了二维→三维的插指结构。化合物2是一个具有6-连接(412·63)拓扑网络的三维框架。化合物4展现了一个基于六核金属簇的(3,4,8)-连接的三维框架。化合物5和8是同构的,具有基于三核金属簇的(3,9)-连接的三维框架结构。化合物6展示了个相对较少的二维→三维的多聚穿套结构。
[Cd(4,4'-tmbpt)(o-bdc)(H2O)]·5.25H2O (1)
[Cd(4,4'-tmbpt)(m-bdc)](2)
[Cd(4,4'-tmbpt)(5-OH-bdc)](3)
[Cd5Na2(4,4'-tmbpt)2(1,2,3-btc)4(H2O)3.5]·6.5H2O (4)
[Cd3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (5)
[Zn(4,4'-tmbpt)(m-bdc)](6)
[Zn3(4,4'-tmbpt)2(m-bdc)3]·5.5H2O (7)
[Zn3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (8)2.含氮多齿配体1-(1H-1,2,4-三唑基甲基)-3-(3-吡啶基)-5-(2-吡啶基)-1,2,4-三唑(简写为2,3'-tmbpt)和1-(1H-1,2,4-三唑基甲基)-3,5-双(3-吡啶基)-1,2,4-三唑(简写为3,3'-tmbpt)和不同的芳香多元羧酸(1,3,5-H3btc=1,3,5-benzenetricarboxylic acid和H4btec=1,2,4,5-benzenetetracarboxylic acid)以及Zn(Ⅱ)离子在水热条件下反应,得到了8个具有各种结构类型的配位聚合物。化合物9和14具有一维的链状结构。化合物10展示了个具有三维CdSO4型网络的二重互穿结构。化合物11展现了一个具有二维sqI型网络的二重互穿结构。化合物12展示了一个具有三维(63)(69·8)拓扑网络的二重互穿结构。化合物13展现了一个具有三维(83)(85·10)拓扑网络的框架结构。化合物15是二维层状结构。化合物16展现了一个具有三维(4·62)(42·68·85)拓扑网络的二重互穿结构。
[Zn(2,3'-tmbpt)(o-bdc)(H2O)] (9)
[Zn(2,3'-tmbpt)(m-bdc)] (10)
[Zn(2,3'-tmbpt)(p-bdc)]·H2O (11)
[Zn2(2,3'-tmbpt)(1,3,5-btc)(OH)]·0.5H2O (12)
[Zn(2,3'-tmbpt)(btec)0.5]·2H2O (13)
[Zn(3,3'-tmbpt)(o-bdc)]·H2O (14)
[Zn(3,3'-tmbpt)(m-bdc)(H2O)]·H2O (15)
[Zn2(3,3'-tmbpt)(1,3,5-btc)(OH)(H2O)] (16)
3.以3,3'-tmbpt,1-(1H-1,2,4三唑基甲基)-3-(4-吡啶基)-5-(3-吡啶基)-1,2,4-三唑(简写为3,4’-tmbpt)和4,4’-tmbpt作为主配体,5-(4’-羧基苄氧基)间苯二酸(简写为H3L)作为为辅助配体,与Ag(Ⅰ)和Cd(Ⅱ)离子反应,得到4个包含金属簇的高连接配位化合物。化合物17具有基于七核单元[Ag7(COO)7]的(3,12)-连接的三维框架。化合物18是基于四核单元[NaCd3(μ3-OH)(COO)5]的(3,4,10)-连接的三维框架。化合物19展示了一个基于双核单元[Cd2(COO)2]的三维(3,4,8)-连接网络。化合物20是一个基于三核单元[Cd3(COO)3]的双节点(3,9)-连接框架。
[Ag7(4,4'-tmbpt)(HL)2(L)(H2O)] (17)
[NaCd3(4,4'-tmbpt)(L)2(OH)]·H20 (18)
[Cd3(3,3'-tmbpt)2(L)2(H2O)2]·3.5H2O (19)
[Cd3(3,4'-tmbpt)2(L)2(H2O)]·15H2O (20)
4.以2,3'-tmbpt、1-(1H-1,2,4三唑基甲基)-3-(4-吡啶基)-5-(2-吡啶基)-1,2,4-三唑(2,4’-tmbpt)、3,3’-tmbpt和3,4’-tmbpt为含氮配体,以八钼酸盐作为阴离子,Ag(Ⅰ)离子作为金属中心,在水热条件下合成了6个配位聚合物。化合物21展示了一个三维(3,4,8)-连接网络,拓扑符号是(4·82)(42·84)(43·820·105)。化合物22展现了一个三维(4,6)-连接的自穿插网络,拓扑符号是(64·82)(42·63·82)(42·68·84·10)。化合物23是一个基于两种不同的八钼酸盐异构体的三维框架。化合物24是由Ag-有机层和[ε-MO8O26]4阴离子构成的三维框架。化合物25展示了一个有趣的一维→二维的多聚穿套结构。化合物26展现了一个二维层状结构。二维层被N-H…O氢键相互作用扩展成一个三维超分子结构。
[Ag2(2,3'-tmbpt)(β-Mo8O26)0.5] (21)
[Ag2(2,4'-tmbpt)2(α-Mo8O26)0.5(H20)0.5]·2H20 (22)
[Ag3(3,3'-tmbpt)2(α-H2Mo8O26)0.5(βMo8O26)0.5] ·3.5H2O (23)
[Ag2(3,3'-tmbpt)(ε-Mo8O26)0.5]·1.75H2O (24)
[Ag2(3,4'-tmbpt)2(β-Mo8O26)0.5]·0.5H20 (25)
[Ag(3,4'-Htmbpt)(βMo8O26)0.5] (26)
The aim of this thesis is to construct a series of coordination polymers with various structures based on several isomers of multidentate N-donor ligands1-((1H-1,2,4-triazol-1-y1)methy1)-3,5-bis(pyridy1)-1,2,-triazole (tmbpt), polycarboxylates/polyoxometalates anions and transition metal ions under hydrothermal conditions. The synthesis conditions, types of topological structures, effects of the structures of organic ligands and the types of metal ions and anions on the structures of the compounds, and the relationship between structures and properties of the compounds have been investigated in detail.
Twenty-six coordination polymers have been hydrothermally synthesized and characterized by infrared spectra (IR), elemental analyses and thermogravimetric (TG) analyses. Moreover, the luminescent properties and photocatalytic behaviors of the compounds have also been investigated.
1. The combination of multidentate N-donor ligand1-((1H-1,2,4-triazol-1-yl)methy1)-3,5-bis(4-pyridyl)-1,2,4-triazole (4,4'-tmbpt) and auxiliary aromatic polycarboxylic acids (o-H2bdc=1,2-benzenedicarboxylic acid, m-Hbdc1,3-benzenedicarboxylic acid,5-OH-H2bdc=5-hydroxy-1,3-benzenedicarboxylic acid,1,2,3-H3btc=1,2,3-benzenetricarboxylic acid and p-H2bdc=1,4-benzenedicarboxylic acid) in the presence of Cd(Ⅱ) and Zn(Ⅱ) ions provides eight coordination polymers. Compounds1,3and7display different2D→3D inter digitated structures. Compound2shows a3D6-connected framework with (412·63) topology. Compound4reveals a3D (3,4,8)-connected net based on hexanuclear units. Compounds5and8are isostructural and display3D (3,9)-connected frameworks based on trinuclear units. Compound6exhibits an unusual2D→3D polythreaded architecture.
[Cd(4,4'-tmbpt)(o-bdc)(H2O)]·5.25H2O (1)
[Cd(4,4'-tmbpt)(m-bdc)](2)
[Cd(4,4'-tmbpt)(5-OH-bdc)](3)
[Cd5Na2(4,4'-tmbpt)2(1,2,3-btc)4(H2O)3.5]·6.5H2O (4)
[Cd3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (5)
[Zn(4,4'-tmbpt)(m-bdc)](6)
[Zn3(4,4'-tmbpt)2(p-bdc)3]·5.5H2O (7)
[Zn3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (8)
2. The mixed ligands of1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-1,2,4-triazole (2,3'-tmbpt) and 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3'-tmbpt) with distinct aromatic polycarboxylic acids (1,3,5-H3btc=1,3,5-benzenetricarboxylic acid and H4btec1,2,4,5-benzenetetracarboxylic acid) in the presence of Zn(Ⅱ) ions afford eight coordination polymers with various structures under hydrothermal conditions. Compounds9and14display1D chain structures. Compound10shows a3D2-fold interpenetrating CdSO4-type framework. Compound11reveals a2D2-fold interpenetrating square layer (sql) structure. Compound12exhibits a3D2-fold interpenetrating framework with (63)(69-8) topology. Compound13shows a non-interpenetrating3D framework with (83)(85-10) topology. Compound15has a2D layer structure. Compound16displays a3D2-fold interpenetrating framework with (4·62)(42·68·85) topology.
[Zn(2,3'-tmbpt)(m-bdc)(H2O)](9)
[Zn(2,3'-tmbpt)(m-dc)](10)
[Zn(2,3'-tmbpt)(m-bdc)]·H2O (11)
[Zn2(2,3'-tmbpt)(1,3,5-btc)(OH)]·0.5H2O (12)
[Zn(2,3'-tmbpt)(btec)o.5]·2H2O (13)
[Zn(3,3'-tmbpt)(o-bdc)]-H2O (14)
[Zn(3,3'-tmbpt)(/m-bdc)(H2O)]·H2O (15)
[Zn2(3,3'-tmbpt)(1,3,5-btc)(OH)(H2O)](16)
3. The reactions of3,3'-tmbpt,1-((1H-1,2,4-triazol-1-yl)-methyl)-3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole)(3,4'-tmbpt) and4,4'-tmbpt with Ag(I) and Cd(II) ions with the help of5-(4'-carboxybenzyloxy)isophthalic acid give four highly connected coordination compounds containing metal clusters. Compound17features a3D (3,12)-connected net based on heptanuclear [Ag7(COO)7] units. Compound18displays a3D (3,4,10)-connected net constructed by tetranuclear [NaCd3(μ3-OH)(COO)5] units. Compound19exhibits a3D (3,4,8)-connected net based on binuclear [Cd2(COO)2] units. Compound20is a3D binodal (3,9)-connected framework constructed by trinuclear [Cd3(COO)4] units.
[Ag7(4,4'-tmbpt)(HL)2(L)(H2O)](17)
[NaCd3(4,4'-tmbpt)(L)2(OH)]-H2O (18)
[Cd3(3,3'-tmbpt)2(L)2(H2O)2]-3.5H2O (19)
[Cd3(3,4'-tmbpt)2(L)2(H2O)]·1.5H2O (20)
4. Six coordination polymers based on multidentate N-donor ligands2,3'-tmbpt,1-((1H-1,2,4-triazol-l-yl)methyl)-3-(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole)(2,4'-tmbpt),3,3'-tmbpt and3,4'-tmbpt, octamolybdates and Ag(I) ions have been synthesized under hydrothermal conditions. Compound21displays a rare3D (3,4,8)-connected net with (4·82)(42·84)(43·820·105) topology. Compound22shows a3D (4,6)-connected self-catenated framework with (64-82)(42-63-82)(42-68-84-10) topology. Compound23is a scarce3D framework based on two different kinds of [Mo8O26]4-isomers. Compound24exhibits a3D framework constructed by silver-organic sheets and the rare [ε-Mo8O26]4-anions. Compound25shows an interesting1D→2D polythreaded structure. Compound26has a2D layer structure, which is linked by the hydrogen bonds to form a3D supramolecular architecture.
[Ag2(2,3'-tmbpt)(β-Mo8O26)0.5](21)
[Ag2(2,4'-tmbpt)2(α-Mo8O26)0.5(H2O)0.5]·2H2O (22)
[Ag3(3,3'-tmbpt)2(α-H2Mo8O26)0.5(β-Mo8O26)0.5]·3.5H2O (23)
[Ag2(3,3'-tmbpt)(ε-Mo8O26)0.5]·1.75H2O (24)
[Ag2(3,4'-tmbpt)2(β-Mo8O26)0.5]·0.5H2O (25)
[Ag(3,4'-Htmbpt)(β-Mo8O26)0.5](26)
[Cd(4,4'-tmbpt)(o-bdc)(H2O)]·5.25H2O (1)
[Cd(4,4'-tmbpt)(m-bdc)](2)
[Cd(4,4'-tmbpt)(5-OH-bdc)](3)
[Cd5Na2(4,4'-tmbpt)2(1,2,3-btc)4(H2O)3.5]·6.5H2O (4)
[Cd3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (5)
[Zn(4,4'-tmbpt)(m-bdc)](6)
[Zn3(4,4'-tmbpt)2(m-bdc)3]·5.5H2O (7)
[Zn3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (8)2.含氮多齿配体1-(1H-1,2,4-三唑基甲基)-3-(3-吡啶基)-5-(2-吡啶基)-1,2,4-三唑(简写为2,3'-tmbpt)和1-(1H-1,2,4-三唑基甲基)-3,5-双(3-吡啶基)-1,2,4-三唑(简写为3,3'-tmbpt)和不同的芳香多元羧酸(1,3,5-H3btc=1,3,5-benzenetricarboxylic acid和H4btec=1,2,4,5-benzenetetracarboxylic acid)以及Zn(Ⅱ)离子在水热条件下反应,得到了8个具有各种结构类型的配位聚合物。化合物9和14具有一维的链状结构。化合物10展示了个具有三维CdSO4型网络的二重互穿结构。化合物11展现了一个具有二维sqI型网络的二重互穿结构。化合物12展示了一个具有三维(63)(69·8)拓扑网络的二重互穿结构。化合物13展现了一个具有三维(83)(85·10)拓扑网络的框架结构。化合物15是二维层状结构。化合物16展现了一个具有三维(4·62)(42·68·85)拓扑网络的二重互穿结构。
[Zn(2,3'-tmbpt)(o-bdc)(H2O)] (9)
[Zn(2,3'-tmbpt)(m-bdc)] (10)
[Zn(2,3'-tmbpt)(p-bdc)]·H2O (11)
[Zn2(2,3'-tmbpt)(1,3,5-btc)(OH)]·0.5H2O (12)
[Zn(2,3'-tmbpt)(btec)0.5]·2H2O (13)
[Zn(3,3'-tmbpt)(o-bdc)]·H2O (14)
[Zn(3,3'-tmbpt)(m-bdc)(H2O)]·H2O (15)
[Zn2(3,3'-tmbpt)(1,3,5-btc)(OH)(H2O)] (16)
3.以3,3'-tmbpt,1-(1H-1,2,4三唑基甲基)-3-(4-吡啶基)-5-(3-吡啶基)-1,2,4-三唑(简写为3,4’-tmbpt)和4,4’-tmbpt作为主配体,5-(4’-羧基苄氧基)间苯二酸(简写为H3L)作为为辅助配体,与Ag(Ⅰ)和Cd(Ⅱ)离子反应,得到4个包含金属簇的高连接配位化合物。化合物17具有基于七核单元[Ag7(COO)7]的(3,12)-连接的三维框架。化合物18是基于四核单元[NaCd3(μ3-OH)(COO)5]的(3,4,10)-连接的三维框架。化合物19展示了一个基于双核单元[Cd2(COO)2]的三维(3,4,8)-连接网络。化合物20是一个基于三核单元[Cd3(COO)3]的双节点(3,9)-连接框架。
[Ag7(4,4'-tmbpt)(HL)2(L)(H2O)] (17)
[NaCd3(4,4'-tmbpt)(L)2(OH)]·H20 (18)
[Cd3(3,3'-tmbpt)2(L)2(H2O)2]·3.5H2O (19)
[Cd3(3,4'-tmbpt)2(L)2(H2O)]·15H2O (20)
4.以2,3'-tmbpt、1-(1H-1,2,4三唑基甲基)-3-(4-吡啶基)-5-(2-吡啶基)-1,2,4-三唑(2,4’-tmbpt)、3,3’-tmbpt和3,4’-tmbpt为含氮配体,以八钼酸盐作为阴离子,Ag(Ⅰ)离子作为金属中心,在水热条件下合成了6个配位聚合物。化合物21展示了一个三维(3,4,8)-连接网络,拓扑符号是(4·82)(42·84)(43·820·105)。化合物22展现了一个三维(4,6)-连接的自穿插网络,拓扑符号是(64·82)(42·63·82)(42·68·84·10)。化合物23是一个基于两种不同的八钼酸盐异构体的三维框架。化合物24是由Ag-有机层和[ε-MO8O26]4阴离子构成的三维框架。化合物25展示了一个有趣的一维→二维的多聚穿套结构。化合物26展现了一个二维层状结构。二维层被N-H…O氢键相互作用扩展成一个三维超分子结构。
[Ag2(2,3'-tmbpt)(β-Mo8O26)0.5] (21)
[Ag2(2,4'-tmbpt)2(α-Mo8O26)0.5(H20)0.5]·2H20 (22)
[Ag3(3,3'-tmbpt)2(α-H2Mo8O26)0.5(βMo8O26)0.5] ·3.5H2O (23)
[Ag2(3,3'-tmbpt)(ε-Mo8O26)0.5]·1.75H2O (24)
[Ag2(3,4'-tmbpt)2(β-Mo8O26)0.5]·0.5H20 (25)
[Ag(3,4'-Htmbpt)(βMo8O26)0.5] (26)
The aim of this thesis is to construct a series of coordination polymers with various structures based on several isomers of multidentate N-donor ligands1-((1H-1,2,4-triazol-1-y1)methy1)-3,5-bis(pyridy1)-1,2,-triazole (tmbpt), polycarboxylates/polyoxometalates anions and transition metal ions under hydrothermal conditions. The synthesis conditions, types of topological structures, effects of the structures of organic ligands and the types of metal ions and anions on the structures of the compounds, and the relationship between structures and properties of the compounds have been investigated in detail.
Twenty-six coordination polymers have been hydrothermally synthesized and characterized by infrared spectra (IR), elemental analyses and thermogravimetric (TG) analyses. Moreover, the luminescent properties and photocatalytic behaviors of the compounds have also been investigated.
1. The combination of multidentate N-donor ligand1-((1H-1,2,4-triazol-1-yl)methy1)-3,5-bis(4-pyridyl)-1,2,4-triazole (4,4'-tmbpt) and auxiliary aromatic polycarboxylic acids (o-H2bdc=1,2-benzenedicarboxylic acid, m-Hbdc1,3-benzenedicarboxylic acid,5-OH-H2bdc=5-hydroxy-1,3-benzenedicarboxylic acid,1,2,3-H3btc=1,2,3-benzenetricarboxylic acid and p-H2bdc=1,4-benzenedicarboxylic acid) in the presence of Cd(Ⅱ) and Zn(Ⅱ) ions provides eight coordination polymers. Compounds1,3and7display different2D→3D inter digitated structures. Compound2shows a3D6-connected framework with (412·63) topology. Compound4reveals a3D (3,4,8)-connected net based on hexanuclear units. Compounds5and8are isostructural and display3D (3,9)-connected frameworks based on trinuclear units. Compound6exhibits an unusual2D→3D polythreaded architecture.
[Cd(4,4'-tmbpt)(o-bdc)(H2O)]·5.25H2O (1)
[Cd(4,4'-tmbpt)(m-bdc)](2)
[Cd(4,4'-tmbpt)(5-OH-bdc)](3)
[Cd5Na2(4,4'-tmbpt)2(1,2,3-btc)4(H2O)3.5]·6.5H2O (4)
[Cd3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (5)
[Zn(4,4'-tmbpt)(m-bdc)](6)
[Zn3(4,4'-tmbpt)2(p-bdc)3]·5.5H2O (7)
[Zn3(4,4'-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (8)
2. The mixed ligands of1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-1,2,4-triazole (2,3'-tmbpt) and 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3'-tmbpt) with distinct aromatic polycarboxylic acids (1,3,5-H3btc=1,3,5-benzenetricarboxylic acid and H4btec1,2,4,5-benzenetetracarboxylic acid) in the presence of Zn(Ⅱ) ions afford eight coordination polymers with various structures under hydrothermal conditions. Compounds9and14display1D chain structures. Compound10shows a3D2-fold interpenetrating CdSO4-type framework. Compound11reveals a2D2-fold interpenetrating square layer (sql) structure. Compound12exhibits a3D2-fold interpenetrating framework with (63)(69-8) topology. Compound13shows a non-interpenetrating3D framework with (83)(85-10) topology. Compound15has a2D layer structure. Compound16displays a3D2-fold interpenetrating framework with (4·62)(42·68·85) topology.
[Zn(2,3'-tmbpt)(m-bdc)(H2O)](9)
[Zn(2,3'-tmbpt)(m-dc)](10)
[Zn(2,3'-tmbpt)(m-bdc)]·H2O (11)
[Zn2(2,3'-tmbpt)(1,3,5-btc)(OH)]·0.5H2O (12)
[Zn(2,3'-tmbpt)(btec)o.5]·2H2O (13)
[Zn(3,3'-tmbpt)(o-bdc)]-H2O (14)
[Zn(3,3'-tmbpt)(/m-bdc)(H2O)]·H2O (15)
[Zn2(3,3'-tmbpt)(1,3,5-btc)(OH)(H2O)](16)
3. The reactions of3,3'-tmbpt,1-((1H-1,2,4-triazol-1-yl)-methyl)-3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole)(3,4'-tmbpt) and4,4'-tmbpt with Ag(I) and Cd(II) ions with the help of5-(4'-carboxybenzyloxy)isophthalic acid give four highly connected coordination compounds containing metal clusters. Compound17features a3D (3,12)-connected net based on heptanuclear [Ag7(COO)7] units. Compound18displays a3D (3,4,10)-connected net constructed by tetranuclear [NaCd3(μ3-OH)(COO)5] units. Compound19exhibits a3D (3,4,8)-connected net based on binuclear [Cd2(COO)2] units. Compound20is a3D binodal (3,9)-connected framework constructed by trinuclear [Cd3(COO)4] units.
[Ag7(4,4'-tmbpt)(HL)2(L)(H2O)](17)
[NaCd3(4,4'-tmbpt)(L)2(OH)]-H2O (18)
[Cd3(3,3'-tmbpt)2(L)2(H2O)2]-3.5H2O (19)
[Cd3(3,4'-tmbpt)2(L)2(H2O)]·1.5H2O (20)
4. Six coordination polymers based on multidentate N-donor ligands2,3'-tmbpt,1-((1H-1,2,4-triazol-l-yl)methyl)-3-(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole)(2,4'-tmbpt),3,3'-tmbpt and3,4'-tmbpt, octamolybdates and Ag(I) ions have been synthesized under hydrothermal conditions. Compound21displays a rare3D (3,4,8)-connected net with (4·82)(42·84)(43·820·105) topology. Compound22shows a3D (4,6)-connected self-catenated framework with (64-82)(42-63-82)(42-68-84-10) topology. Compound23is a scarce3D framework based on two different kinds of [Mo8O26]4-isomers. Compound24exhibits a3D framework constructed by silver-organic sheets and the rare [ε-Mo8O26]4-anions. Compound25shows an interesting1D→2D polythreaded structure. Compound26has a2D layer structure, which is linked by the hydrogen bonds to form a3D supramolecular architecture.
[Ag2(2,3'-tmbpt)(β-Mo8O26)0.5](21)
[Ag2(2,4'-tmbpt)2(α-Mo8O26)0.5(H2O)0.5]·2H2O (22)
[Ag3(3,3'-tmbpt)2(α-H2Mo8O26)0.5(β-Mo8O26)0.5]·3.5H2O (23)
[Ag2(3,3'-tmbpt)(ε-Mo8O26)0.5]·1.75H2O (24)
[Ag2(3,4'-tmbpt)2(β-Mo8O26)0.5]·0.5H2O (25)
[Ag(3,4'-Htmbpt)(β-Mo8O26)0.5](26)
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