【作者】 吴华；

【导师】 马建方；

【作者基本信息】 东北师范大学 ， 无机化学， 2011， 博士

【摘要】 本论文主要研究了三齿配体—三(4-咪唑基苯)胺(简写为Tipa)与过渡金属离子合成的具有多种新颖的网络拓扑结构类型,研究这些化合物的合成条件及规律,分析这些化合物网络所属的拓扑及缠结结构类型,同时考察了辅助配体对于整个网络拓扑的影响规律,探究分子自组装原理,探索新类型的缠结网络,努力寻找拓扑类型和结构的内部联系,预言新型缠结网络和拓扑类型的形成、以及新物质结构和性能间的关系。利用水热技术合成方法,合成了19个新型的基于金属-有机网络构筑的高维网络结构,通过元素分析、IR、XRPD、TG和单晶X-射线衍射对晶体结构进行了表征,对—些化合物的热稳定性和荧光性质进行了初步研究。1.利用三(4-咪唑基苯)胺三齿配体、过渡金属离子及不同的羧酸阴离子在水热条件下得到了4个高维的化合物。化合物1是(3,5)连接(42·6)(42·67·8)的2D层状拓扑结构。化合物2是由具有44拓扑层形成的2D→3D结构。化合物3是(3,4)连接的(5·62·82·9)(63·72·9)(73)(62·8)的3D网络拓扑结构。化合物4是具有(3,4,6)连接的(42·62·7.8)(4·6·83·10)(6·8·10)(44·52·67·7·8)(42·82·102)的3D网络拓扑结构。[Mn(Tipa)(m-bdc)·H2O (1) [Zn(Tipa)(m-bdc)]·H2O (2) [Zn2(Tipa)(btc)(μ2-O)]·2H2O (3) [Zn2(Tipa)(btca)]·3.5H2O (4)2.在水热条件下,利用三(4-咪唑基苯)胺配体、不同的阴离子和过渡金属合成了4个3D的互穿缠结网络。化合物5是一个3D的(3,5)连接的(63)(65·85)的二重互穿网络。化合物6是4重互穿的(10,3)-b拓扑网络结构。化合物7是(3,4)连接的(4·82)(4·85)的以2+2形式互穿的四重互穿网络。化合物8是一例极其罕见的54重互穿的(10,3)-a拓扑网络。[Cd(Tipa)(NH2-bdc)]·CH3OH·H2O (5) Cd(Tipa)(badc)(H2O) (6) [Ni2(Tipa)2(p-bdc)(H2O)2]2·Cl4·4H2O (7) [Ag3(OH)(H2O)2(Tipa)2.5] [Mo2O7]·4.5H2O (8)3.结合三(4-咪唑基苯)胺配体,合理选择阴离子和过渡金属,利用分子识别和自组装原理成功合成了6个新缠结类型的金属-有机网络结构。化合物9和10都是2D→2D聚轮烷网络,游离的羧酸有机配体夹在聚轮烷层中间。化合物11和12是类似的2D→3D的聚轮烷网络结构。化合物13是一例极为特殊的配合物,具有2D→2D和2D→3D两种线穿特征的聚轮烷网络结构。化合物14是以平行方式穿插的2D→3D聚轮烷网络。[Ni2(Tipa)2(p-bdc)(H2O)4]·(p-bdc)·0.5H2O (9) [Cu2(Tipa)2(p-bdc)(CH3OH)(H2O)]·(p-bdc)·1.5(CH3OH)·4.5(H2O) (10) [Cd(Tipa)(NH2-bdc)2]·H2O (11) [Mn(Tipa)(NH2-bdc)2]·H2O (12) [Ni2(Tipa)2(p-bdc)2(H2O)2]·2.25H2O (13) [Cd(Tipa)Cl2]·H2O (14)4.利用对苯二甲酸阴离子和三(4-咪唑基苯)胺配体,在水热条件下变换过渡金属离子,得到了2个新颖的具有自穿插的新类型缠结互穿网络结构。化合物15是3D的二重互穿结构,单一的3D网络结构是具有轮烷和自穿插特性的网络。化合物16同样是具有轮烷特性的3D二重互穿的自穿插的(4·62)(42·54·62·75·72·92)(52·66·75·82)网络。[Cd3(Tipa)2(p-bdc)2Cl2]·4H2O (15) [Co3(Tipa)2(p-bdc)3] (16)5.利用三(4-咪唑基苯)胺配体和多元羧酸阴离子—1,2,3-苯三酸,在水热条件下合成了3个含有金属簇的化合物。化合物17是由Tipa配体连接五核锌簇和锌-氧链形成的3D网络。化合物18是基于三核镉簇的3D网络,其网络可归结为(3,6)连接(63)(44·611)拓扑。化合物19是基于十二核镉簇的3D网络,其网络可归结为10连接的312·426.57拓扑。[Zn7.5(Tipa)(1,2,3-bta)4(OH)3]·4H2O (17) [Cd3(Tipa)2(1,2,3-bta)2]·2.5H2O (18) [(Cd6(Tipa)2(1,2,3-bta)3(H2O)3]·3H2O (19)更多还原

【Abstract】 The aim of this thesis is the study of new coordination compounds based on tridentate tri(4-imidaolyphenyl)amine ligand and transition metal ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out.Nineteen new coordination compounds have been synthesized on the basis of hydrothermal technique and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities properties and fluorescent properties of some compounds have been studied.1. Four compounds based on tri(4-imidaolyphenyl)amine and different carboxylates have been synthesized. Compound 1 shows a 2D wave layer with (3,5)-connected (42·6)(42·67·8) topololgy. Compound 2 is a 2D→3D network with 44 topological layers. Compound 3 exhibits 3D framework with (3,4)-connected (5·62·82·9)(63·72·9)(73)(62·8) topology. Compound 4 is a 3D framework with (3,4,6)-connected (42·62·7·8)(4·6·83·10)(6·8·10)(44·52·67·7·8)(42·82·102) topology. [Mn(Tipa)(m-bdc)]·H2O (1) [Zn(Tipa)(m-bdc)]·H2O (2) [Zn2(Tipa)(btc)(μ2-O)]·2H2O (3) [Zn2(Tipa)(btca)]·3.5H2O (4)2. Four entangled coordination polymers based on tri(4-imidaolyphenyl)amine ligand and different carboxylates have been synthesized under hydrothermal condition. Compound 5 shows a 2-fold interpenetrated 3D framework with (3,5)-connected (63)(65·85) topology. Compound 6 is a 4-fold interpenetrated 3D framework with (10,3)-a topology. Compound 7 exhibits (3,4)-connected (4·82)(4·85) topological 3D network, where four independent networks interpenetrate each other to form a 4-fold interpenetation. Compound 8 is a fascinating 54-fold interpentration with (10,3)-a topology. [Cd(Tipa)(NH2-bdc)]·CH3OH·H2O (5) Cd(Tipa)(badc)(H2O) (6) [Ni2(Tipa)2(p-bdc)(H2O)2]2·Cl4·4H2O (7) [Ag3(OH)(H2O)2(Tipa)2.5][Mo2O7]·4.5H2O (8)3. Six new entangled polythreaded networks based on tri(4-imidaolyphenyl)amine ligand, different anions and transition metal ions have been synthesizd. Compounds 9 and 10 are 2D→2D polyrotaxane networks, where the free carboxylate anions sandwiching between polyrotaxane layers. Compounds 11 and 12 show the 2D→3D polyrotaxane frameworks. Compound 13 is a special polyrotaxane framework with both 2D→2D and 2D→3D features. Compound 14 is the first example of 2D→3D polyrotaxane in parallel fashion. [Ni2(Tipa)2(p-bdc)(H2O)4]·(p-bdc)·0.5H2O (9) [Cu2(Tipa)2(p-bdc)(CH3OH)(H2O)]·(p-bdc)·1.5(CH3OH)·4.5(H2O) (10) [Cd(Tipa)(NH2-bdc)2]·H2O (11) [Mn(Tipa)(NH2-bdc)2]·H2O (12) [Ni2(Tipa)2(p-bdc)2(H2O)2]·2.25H2O (13) [Cd(Tipa)Cl2]·H2O (14)4. Two interesting self-penetrating networks based on p-bdc anion, tri(4-imidaolyphenyl)amine ligand and metals have been synthesized under the hydrothermal condition. Compound 15 is a 3D self-penetrating framework with polyrotaxane feature, where two 3D frameworks interpenetrate each other to form a 2-fold interpentration. Compound 16 is a 3D self-penetrating framework with (4·62)(42·54·62·75·72·92)(52·66·75·82) topology, where two 3D frameworks interpenetrate each other to form a 2-fold interpentration. [Cd3(Tipa)2(p-bdc)2Cl2]·4H2O (15) [Co3(Tipa)2(p-bdc)3] (16)5. Three compounds based on 1,2,3-bta anion, tri(4-imidaolyphenyl)amine ligand and different metals have been synthesized under hydrothermal condition. For compound 17, tri(4-imidaolyphenyl)amine ligands connected pentanuclear ZnⅡclusters and ZnⅡ-O chains to form an infinite 3D framework. Compound 18 is a 3D framework with (3,6)-connected (63)(44·6n) topology based on trinuclear CdⅡcluster. Compound 19 is a novel 3D framework based on dodecanuclear CdⅡcluster with (3,6)-connected (63)(44·611) topology. [Zn7.5(Tipa)(1,2,3-bta)4(OH)3]·4H2O (17) [Cd3(Tipa)2(1,2,3-bta)2]·2.5H2O (18) [(Cd6(Tipa)2(1,2,3-bta)3(H2O)3]·3H2O (19)更多还原