以有机多羧酸类配体构筑新型金属—有机配位聚合物的结构、表征及性质

【作者】 郝娜；

【导师】 沈恩洪； 王恩波；

【作者基本信息】 东北师范大学 ， 无机化学， 2004， 硕士

【摘要】 本论文利用几种不同的有机多羧酸类配体为基本构筑单元，通过各种有机含N配体的“修饰”或“桥连”，构筑新型的金属-有机配位聚合物，研究这类化合物的合成条件及规律。利用水热技术和有机溶剂合成方法，合成了7种新型金属-有机配位聚合物和2种新型金属氧簇化合物，通过元素分析，IR，EPR，XPS，TG，51V NMR和单晶X-射线衍射对晶体结构进行了表征，对化合物的热稳定性、荧光特性进行了初步研究。1．通过引入1,2,4-苯三甲酸(H3btc)和1,2,4,5-均苯四甲酸(H4btc)，水热和溶剂热合成和结构表征了3种新型的金属-有机配位聚合物：{[Co(H2O)2][Co2(phen)2(btc)2]}n (1){[Fe(phen)(btc)(OH2)]2·CH3CH2OH}n (2)[Cu2(2,2’-bipy)2(btec)]n (3)化合物1、2和3表现出不同的特点，发现使用具有不同配位的后过渡金属及羧酸配体，对化合物的自组装有显著影响；化合物(1)是具有一个新颖的二维(4,6)-格子型网络；化合物(2)是一个新颖的由1,2,4-苯三甲酸构成的金属-有机超分子骨架；化合物(3)是一个新的以1,2,4,5-均苯四甲酸(H4btc)构筑的具有一维的梯形链状结构。2．利用草酸为基本建筑单元，在水热条件下自组装形成1种新型后过渡金属-草酸杂化化合物，并进行了晶体结构表征：[Zn3(C2O4)3(4,4’-bipy)4]2n (4)化合物(4)具有一种有趣的二维层状网络结构，由草酸锌的链和有机4,4’-bipy配体构成。3．利用己二酸为构筑单元，引入不同含N配体，借助水热合成技术合成并表征了3种新型的金属-有机配位聚合物，并进行了晶体结构表征：[Co(OOC(CH2)4COO)(4,4’-bipy)] (5){Cd[O2C(CH2)4CO2][1,10’-phen]}n (6) <WP=4>{Cd2(C2O4)[O2C(CH2)4CO2(OH2)2][2,2’-bipy]}?H2O (7)化合物(5)具有一种新颖的三维互穿骨架；化合物(6)是一个一维链状聚合物，代表第一个由混合的己二酸和1,10’-phen配体所连接而成的双核化合物；化合物(7)呈现一个有趣的三维网络结构，代表了第一例将2,2’-bipy和草酸基团引入到{M/adipate}体系中。而且草酸配体的引入使得金属-己二酸配位聚合物的维度发生变化。荧光性质研究表明，化合物6和7可能是潜在的荧光材料。4．在水热条件下合成2种新型金属氧簇化合物，并进行了晶体结构表征：(H3O)3[AsMo12O40(VO)6]·6H2O (8)(NH4)4[H12VV12O36(VIVO4)]·11H2O (9)化合物(8)是第一个具有六帽Keggin型结构的钼钒砷酸盐化合物。化合物(9)是第一个具有具有Keggin型结构的多钒酸盐。更多还原

【Abstract】 The aim of this thesis is the synthesis of new metal-organic coordination polymers on the basis of organic multi-carboxylate ligands, which are “decorated” or “bridged” by various organic N-donor ligands. The study on synthetic conditions and rules for these hybrid compounds for these compounds are also carried out.Seven new metal-organic coordination polymers and two novel metal-oxo clusters compounds have been synthesized on the basis of hydrothermal technique and/or organic solvent synthesis methods and structurally characterized by elemental analyses, IR, EPR, XPS, TG, 51V NMR and single crystal X-ray diffractions. The thermal stabilities, fluorescent properties of these compounds have been studied.1. Three new metal-organic coordination polymers have been hydrothermally synthesized by the introduction of 1,2,4-H3btc and 1,2,4,5-H4btc and structurally characterized:{[Co（H2O）2][Co2（phen）2（btc）2]}n （1）{[Fe（phen）（btc）（OH2）]2·CH3CH2OH}n （2）[Cu2（2,2’-bipy）2（btec）]n （3）Compounds （1）³ exhibit different structural characteristics. It is found that the use of carboxylate ligands and different latter transition metals may influence the self-assembly of the compounds. Compound （1） exhibits a novel two-dimensional network with unusual （4,6）-lattice-type network, and H3btc ligands connect the metal centers to form one dimer. Compound （2） possess a novel metal-organic supramolecular framework constructed by 1,2,4-H3btc. Compound （3） represents a new infinite 1-D ladderlike chain architecture constructed from btec ligands.2. One new latter transition metal-oxalate hybrid compounds have been synthesized in the hydrothermal condition by virtue of oxalate building <WP=6>blocks. The crystal structures have been characterized:[Zn3（C2O4）3（4,4’-bipy）4]2n （4）Compound （4） exhibits a novel two-dimensional network which consists of infinite zinc （II） oxalate chains connected to each other by bridging and terminal ligand 4,4’-bipy ligands alternately.3. Three new metal-organic coordination polymers have been hydrothermally synthesized on the basis of adipate ligands and the introduction of different N-donors. The crystal structures have been characterized: [Co（OOC（CH2）4COO）（4,4’-bipy）] （5）{Cd[O2C（CH2）4CO2][1,10’-phen]}n （6）{Cd2（C2O4）[O2C（CH2）4CO2（OH2）2][2,2’-bipy]}?H2O （7）Compound （5） exhibits a novel three-dimensional interpenetrating network. Compound （6） possesses a novel one-dimensional chain, and represents the first dinuclear compound connected by the mixed adipate and 1,10’-phen ligands. Compound （7） exhibits an interesting 3-D network and represents the first example in which both 2,2’-bipy and oxalate group are introduced into the {M/adipate} system. Furthermore, the introduction of oxalate ligand has led to the dimensional transformation of the metal-adipate coordination polymers.These observations indicate that compounds （6） and （7） maybe excellent candidates for photoluminescence materials.4. Two new metal-oxo clusters compounds have been hydrothermally synthesized and structurally characterized:（H3O）3[AsMo12O40（VO）6]·6H2O （8）（NH4）4[H12VV12O36（VIVO4）]·11H2O （9）Compound （8） is the first hexacapped Keggin-type molybdovandoarsenate. Compound （9） is the first Keggin-type polyvanadate.更多还原