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你可能喜欢上传用户：flatlxxbxt资料价格：5财富值&&『』文档下载 ：『』&&『』学位专业：&关 键 词 ：&&&&&权力声明：若本站收录的文献无意侵犯了您的著作版权，请点击。摘要:（摘要内容经过系统自动伪原创处理以避免复制，下载原文正常，内容请直接查看目录。）本论文努力于应用双功效刚性含N配体，d10金属离子和事后制备的多金属氧酸盐修建新鲜的多金属氧酸盐基的无机一无机杂化化合物，研讨这类化合物的分解前提及纪律，分离商量了配体的长度、多金属氧酸盐阴离子的类型和反响系统的酸碱度对构造构成的影响。应用份子自组装道理，摸索新物资构造和反响物机能的关系，拓宽现有的认知规模，为多金属氧酸盐衍生物的定向分解供给实际和试验数据。本文选用双功效刚性含N配体酚嗪(phnz)，4，4’一联吡啶(4，4’一bipy)和1， 2一二(4一吡啶)乙烯(bpe)为无机组分，各类多金属氧酸盐阴离子和d10金属盐为无机组分，应用水热分解技巧，经由过程转变反响原料的类型和反响系统的pH值分解了22种未见文献报导的金属一无机含N配位聚合物润饰的多金属氧酸盐衍生物，经由过程元素剖析、IR、TG、XPRD，XPS和单晶X一射线剖析对这些晶体的构造停止了表征，并对部门化合物停止了电化学性质的初步研讨。重要研讨成果以下1。用雷同的过渡金属配位聚合物链{Cu一4，4’一bipy}去润饰雷同类型分歧体积和分歧类型的多金属氧酸盐，在水热前提下，分解并表征了6个多重Cu一bipy聚合物链润饰的多金属氧酸盐衍生物。化合物1一3是用Cu一bipy链润饰雷同类型(Keggin型)分歧体积的多金属氧酸盐的衍生物，它们代表了第一例应用统一三金属簇上的线形分列的Od…Ob…Od原子与金属配位的多金属氧酸盐衍生物。化合物1是三重Cu一bipy链润饰的Mo系Keggin型多金属氧酸盐的1D构造；2和3是同构的，是四重Cu一bipy链润饰的W系Keggin型多金属氧酸盐的2D构造，他们构造的分歧解释经由过程微调Keggin型多金属氧酸盐的体积可以转变多金属氧酸盐与Cu一bipy链的键连方法。化合物4一6是Cu一bipy链润饰分歧类型的多金属氧酸盐的衍生物，4是四重Cu一bipy链润饰的Lindqvist型多金属氧酸盐的2D构造；5是第一例3D的Wells一Dawson型多金属氧酸盐的衍生物，表示出四重Cu一bipy链润饰多金属氧酸盐的3D构造；6是无穷重Cu一bipy链润饰的同多金属氧酸盐的3D构造。经由过程考核化合物1一6的构造，我们信任多金属氧酸盐的体积和类型关于Cu一bipy链润饰的多金属氧酸盐衍生物的构造的构成长短常主要的。2。以Keggin型多金属氧酸盐为修建单位，经由过程引入分歧单元长度的Cu一N金属配位聚合物链，在水热前提下，分解并表征了5个多重Cu一N金属配位聚合物链润饰的多金属氧酸盐衍生物。化合物7一9是用分歧单元长度的Cu一N金属配位聚合物链润饰Keggin型多金属氧酸盐的衍生物。化合物7展示了三重Cu一N聚合物链润饰的多金属氧酸盐的1D单拉锁构造，多金属氧酸盐以“高低”情势分列在1D链的双方。化合物8是二重Cu一N链润饰的多金属氧酸盐的构造，Keggin型多金属氧酸盐以“肩并肩”情势分列在1D梯子链的中央。化合物9具有超份子1D梯子构造。这些构造解释了分歧单元长度的Cu一N金属配位聚合物链包容多金属氧酸盐的才能是分歧的，从而招致两者之间的键连方法和构造的分歧。在雷同分解前提应用分歧长度的配体的情形下化合物10和11展现了{AsMo12O40}多金属氧酸盐的润饰化学。10显示了润饰双钒帽Keggin型金属氧酸盐衍生物的最高维度和最高衔接数。经由过程转变配体的长度，1D梯子构造的11被取得，它们的胜利分别再一次丰硕了水热掌握分解的数据。3。以Wells一Dawson型多金属氧酸盐、Ag盐和bipy份子为修建单位，经由过程调理反响系统的pH值，水热分解和构造表征了四个基于Wells一Dawson型的多金属氧酸盐的衍生物。化合物是在雷同的分解前提然则分歧的pH规模内取得的，pH值在这四个化合物的组装进程中起到了决议感化。因为Ag源对pH值的选择性，经由过程调理反响的pH值，在较高的酸度下3D多重Ag一N配位聚合物链润饰的Wells一Dawson型多金属氧酸盐衍生物12和13被取得。化合物12具有(4·4)衔接的NbO拓扑，拓扑符号为(64·82)(64·82)。化合物13具有(92·12)(8·104·12)(32·102·112)(3·6·102·122)拓扑的收集，表示了润饰的Wells一Dawson型多金属氧酸盐的最高衔接。经由过程持续下降系统的酸度，Ag源下降或许消逝招致Ag离子和bipy份子的配位才能下降；另外一方面在酸性规模内跟着pH的降低，bipy份子的质子化趋向加强也下降了与Ag离子的配位，两者一路终究招致超份子化合物14和15被取得。4。以多金属氧酸盐和M一N金属配位聚合物为修建单位，应用自组装道理，在水热前提下目的分解并表征了5个高维高衔接的多金属氧酸盐衍生物。化合物16一20都是具有最高维度(3D)最高衔接数的多金属氧酸盐的衍生物。16一19是同构的，是一个(4·6)混衔接的3D收集，该收集的拓扑符号为(41·64·81)(42·63·810)，个中Keggin型多金属氧酸盐作为六齿无机配体与四周的金属配位，是今朝报导的润饰的Keggin型多金属氧酸盐的最高衔接。化合物20是一个(3·4·6)混衔接的3D收集，该收集的拓扑符号为(3·7·8)(63·8)(64·82)(64·82) (32·4·75·82·9·10)，个中Wells一Dawson型多金属氧酸盐作为九齿无机配体与四周的金属配位，也显示了到今朝为止润饰的Wells一Dawson型多金属氧酸盐的最高衔接。5。以Lindqvist型多金属氧酸盐为模版，经由过程引入铜一酚嗪合营物修建了两个以Lindqvist型多金属氧酸盐为模版的具有孔洞的三维配位聚合物。化合物21和22是以Lindqvist型多金属氧酸盐为模板修建的具有孔洞的三维配位聚合物，是多酸阴离子经由过程氢键衔接二维金属一无机收集构成的，多酸阴离子位于孔洞内。21和22的胜利制备注解了一种修建具有孔洞的POM份子基配位聚合物的自组装办法。因为金属一无机聚合物和POM构造的多样性，只需选择适合的POM单位和金属一无机亚构造，可制得一批构造新鲜的具有孔洞的POM份子基配位聚合物，从而丰硕以POM为基本的杂化资料。Abstract:The effort in the application of double effect of rigid ligands containing N, d10 metal ion and afterwards of preparation of metal - oxygen acid salts build fresh polymetallic oxygen sour base inorganic organic hybrid compounds, compounds of this kind of research is premise disassembling and discipline, separation and discuss the ligand length, metal - oxygen acid salt anion type and reaction system pH on the structure. The application part of self assembling reason, explore new material structure and the relationship of reactant function, broaden the awareness of the existing scale, the actual supply of decomposition and experimental data for directional polyoxometalate derivatives. Compounds and transformation of water (phnz rigid selection of the double effect of N-containing ligands phenolic triazine and 4, 4 '- bipyridine (4, 4' - bipy) and 1, 2, 12 (4 pyridyl) ethylene (BPE) as inorganic components, all kinds of polymetallic oxygen sour salt anion and d10 metal salt as the inorganic component, the application of thermal decomposition technique, through the process of reaction raw material type and reaction system pH value decomposition 22 which had not been reported in the literature of metal inorganic nitrogen coordination polymers retouching polymetallic oxygen acid salt derivatives by element analysis, IR, TG, xprd, XPS and single crystal X ray analysis of the crystal structure of the characterization of the Department to stop the electrochemical properties of the preliminary discussion. The following 1 important results. With the same transition metal coordination polymer chain {Cu 4, 4 'bipy} to retouch similar types of different volume and different types of metal - oxygen acid salts, under hydrothermal conditions, decomposition and characterized six multiple Cu bipy polymer chain retouch the polymetallic oxygen acid salts derivatives. Compounds 1 3 is Cu bipy chain retouch the same volume of different types (Keggin type polyoxometalate acid salt derivatives. They represent the first case of using unified breakdown of the three metal cluster on the alignment of OD. Ob... Polyoxometalate derivatives of the Od atoms and metal coordination. Compound 1 is a 1D structure of triple Cu bipy chain retouching Mo Keggin type polyo 2 and 3 are isomorphic is 2D structure of four Cu bipy chain retouching w Keggin type polyoxometalate acid salt and their structural differences explain through the volume of the trimming process of Keggin type polyoxometalate acid salt can change the polymetallic oxygen sour salt and Cu a bipy chain key connection method. Compounds 4 to 6 is Cu bipy chain polishing different types of metal oxygen acid salts derivatives and 4 is the 2D structure of four Cu bipy chain retouching Lindqvist type polymetall 5 is derivative of the first cases of 3D wells Dawson type polyoxometalate acid salt, said the 3D structure of four Cu bipy chain retouching polymetall 6 is infinite heavy Cu bipy chain retouching with polymetallic oxygen acid salts of 3D structure. Through the construction of assessment of process of compounds 1 6, we trust length volume and type polyoxometalates on Cu bipy chain polishing metal - oxygen acid salt derivatives structure composition is very important. 2. With Keggin type polyoxometalate acid salt for construction unit, through the introduction of different unit length of Cu n metal coordination polymers chain, under hydrothermal conditions, the decomposition and characterized 5 multiple Cu n metal coordination polymers chain retouch the polymetallic oxygen acid salts derivatives. Compound 7 9 is a unit of length Cu with different N metal coordination polymer chain Keggin polyoxometalate derivatives. Compound 7 has triple Cu n polymer chain retouch the polymetallic oxygen acid salts of 1D single zipper structure, polyoxometalates to &high-low& situation breakdown in the 1D chain of both sides. Compound 8 is a structure of double Cu n chain retouch the polymetallic oxygen acid salts and Keggin type polyoxometalate acid salt to &shoulder to shoulder& situation breakdown in the center of the 1D ladder chains. Compound 9 has a super 1D ladder structure. These differences in structural interpretation of unit length Cu N metal coordination polymer chain containing polyoxometalates can be different, resulting in between the bonding method and structural differences. In the same decomposition under the premise of using different length of ligand compounds 10 and 11 show the polishing chemistry of acid {AsMo12O40} oxygen than metal salt. 10 shows the highest dimension of Polish double vanadium capped Keggin type polyoxometalate derivatives and the highest connection number. Through the process of changing the length of ligand, 1D ladder structure of 11 is achieved, they were once again great victory data in the hands of hydrothermal decomposition. 3. Wells Dawson type polyoxometalate acid salt, Ag salt and bipy molecules for the construction unit, through the process of conditioning reaction system pH value, water thermal decomposition and structural characterization of the four based on the wells Dawson type polyoxometalate acid salt derivatives. Compound is made in the same premise but different decomposition of the pH range, the pH value plays a role in the process of Assembly resolution four compounds. Because of the selectivity of Ag sources on pH value, by conditioning the repercussions of the pH value, in the higher acidity 3D multiple Ag n with a polymeric chain retouching of wells Dawson type polyoxometalate acid salt derivatives 12 and 13 were made. Compound 12 (4 / 4) NbO topological connection, topology (64 - 82) (64 - 82). Compound 13 with (92 - 12) (8 - 104 - 12) (32 - 102 - 112) (3 - 6 - 102 - 122) collected topology, said the highest cohesion retouching wells Dawson type polyoxometalate acid salt. Through the process of continuous decline system acidity and decreased Ag source may die resulted in low Ag ions and the memb also in the acidic range follow pH reduction and bipy molecules of protonated trend strengthen also decreased with the Ag ion coordination, both eventually lead to super molecular compound 14 and 15 were obtained. 4. Based on polyoxometalates M and N metal coordination polymers for the construction unit, the application of self-assembly in water under the premise of reasonable, thermal decomposition and characterization of 5 Gao Weigao convergence of polyoxometalate derivatives. Compound 16 is 20 with the highest dimension (3D) polyoxometalate derivatives of the highest connection number. 16 to 19 are isomorphic, is a 4 (- 6) mixed collection of 3D interface, collection of the topological symbol (41, 64, 81) (42, 63, 810), medium Keggin type polyoxometalate acid salt as six tooth inorganic ligands around the metal coordination is highest cohesion today reported that touches the Keggin type multi metal oxygen acid salts. Compound 20 is a (3 - 4 - 6) mixed cohesive 3D collected, the collected topology symbol for (3, 7, 8) (63 - 8) (64 - 82) (64 - 82) (32 - 4 - 75 - 82 - 9 - 10), one of the wells Dawson type polyoxometalate acid salt as nine tooth inorganic ligands around the metal with a, also shows the highest cohesion to now retouch the wells Dawson type polyoxometalate acid salt. 5. The Lindqvist type polyoxometalates as a template, through the process of introducing a joint venture built in copper phenol two Lindqvist type polyoxometalates as a template with holes in the three-dimensional coordination polymers. Compound 21 and 22 is constructed with Lindqvist type polymetallic oxygen sour salt as the template with holes in the three-dimensional coordination polymer, acid anions through hydrogen bonding cohesion 2D metal inorganic collection consisting of the and polyoxoanions in holes. 21 and 22 of the preparation of a victory notes built with self-assembled POM member base hole way of coordination polymers. Because of the diversity of a metal inorganic polymer and POM structure, simply select the suitable POM units and metal inorganic sub structure, of a group of structural holes POM molecules ligand coordination polymers with fresh, and rich in POM is the basic hybrid material.目录:中文摘要4-7英文摘要7-9第一章 前言12-46&&&&1 多金属氧酸盐概况13-14&&&&2 孤立的多金属氧酸盐簇的结构及其合成研究14-23&&&&3 多金属氧酸盐的修饰和功能化研究23-37&&&&4 选题依据和研究目的37-38&&&&5 试剂和分析仪器38-39&&&&参考文献39-46第二章 相同单位长度Cu-bipy链修饰不同多金属氧簇的衍生物研究46-68&&&&1 引言46-47&&&&2 Cu-bipy链修饰的Keggin型多金属氧簇的衍生物合成、表征和性质研究47-58&&&&3 Cu-bipy 链修饰的其它类型多金属氧酸簇的衍生物合成、表征和性质研究58-66&&&&4 结论66-67&&&&参考文献67-68第三章 不同单位长度Cu-N 链修饰Keggin 型多金属氧簇的衍生物研究68-88&&&&1 引言68-69&&&&2 不同长度Cu-N 链修饰Keggin 型多金属氧簇的衍生物合成、表征和性质研究69-77&&&&3 不同长度 Cu-N 链修饰双帽 Keggin 型多金属氧簇的衍生物合成、表征和性质研究77-86&&&&4 结论86-87&&&&参考文献87-88第四章 pH 对合成Ag-bipy 链修饰 Wells-Dawson 型多金属氧簇的衍生物的影响的研究88-104&&&&1 引言88-89&&&&2 合成89-90&&&&3 单晶X-ray结构分析与讨论90-96&&&&4 表征96-98&&&&5 电化学性质的研究98-100&&&&6 抗菌测试100-101&&&&7 结论101-102&&&&参考文献102-104第五章 高维、高连接的多金属氧簇衍生物的合成研究104-126&&&&1 引言104-105&&&&2 高维、高连接的众ggjn型多金属氧簇衍生物的目标合成、表征和性质研究105-114&&&&3 高维、高连接的D~on型多金属氧簇衍生物的目标合成、表征和性质研究114-123&&&&4 结论123-124&&&&参考文献124-126第六章以Undqvist型多金属氧簇为模版构筑具有孔道结构的配位聚合物的合成和表征126-134&&&&1 前言126-127&&&&2 合成127&&&&3 单晶 X-ray 结构分析和讨论127-131&&&&4 表征131-132&&&&5 结论132-133&&&&参考文献133-134结论134-138致谢138-139在学习期间公开发表论文情况139-140分享到：相关文献|本论文选用多金属氧酸盐为基本建筑单元，选择不用的有机配体跟金属Cu原子在离子热的条件下合成了一系列结构新颖性质优异的多金属氧酸盐基无机-有机杂化材料，并且探讨了不同反应条件（反应的酸碱度，不同刚柔性的有机配体）对化合物的结构以及性质的影响，并且深入的研究了化合物的潜在应用。本文利用离子热的方法通过调节不同的反应条件跟不同的反应物比例还有不同的有机配体，合成了13种基于多金属氧酸盐的无机-有机杂化材料。本文通过元素分析、红外光谱、热重分析、光电子能谱、X-射线粉末衍射、单晶X-射线衍射、紫外可见光谱、扫描电子显微镜、高分辨质谱、核磁、气体吸附仪、气相色谱、液相色谱、电化学工作站等手段对化合物的结构跟性质进行了表征，并且对化合物的光催化活性，离子交换性质，气体吸附性质进行了初步的研究。1.以Wells-Dawson型多金属氧酸盐为基本结构单元选用不同的溶剂，基于溶剂的结构效应合成并表征了2个超分子化合物。（H$$sub$$2$$/sub$$BBI）$$sub$$3$$/sub$$P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$·H$$sub$$2$$/sub$$O （1）H$$sub$$2$$/sub$$（H$$sub$$2$$/sub$$BBI）$$sub$$2$$/sub$$P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$·2H$$sub$$2$$/sub$$O （2）在化合物1到2中反应的初始原料都是相同的，通过选用不同性质的溶剂，在水热跟离子热的条件下合成了两个基于经典多金属氧酸盐结构的超分子化合物，化合物1在水热的条件下形成了结构新颖的三维超分子结构，而通过改变溶剂，换用离子热条件，选用相同的初始原料，化合物由于溶剂的结构效应使化合物2结晶在手性空间群中，得到了一个外消旋、超分子化合物。实现了不同的溶剂到不同空间群的转表。2.以Wells-Dawson型多金属氧酸盐作为次级结构建筑单元选择不同刚性以及柔性的有机配体跟+2价Cu离子，在离子热的条件下合成并表征了结构新颖的5个杂化化合物。H$$sub$$3$$/sub$$（Tea）（Bmim）$$sub$$3$$/sub$$[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]·3H$$sub$$2$$/sub$$O （3）Cu$$sup$$II$$/sup$$（Bbi）$$sub$$1.5$$/sub$$（H$$sub$$2$$/sub$$Bbi）$$sub$$2$$/sub$$[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]（4）Cu$$sup$$II$$/sup$$$$sub$$2.5$$/sub$$（Mimin）（HMimin）（Bbi）$$sub$$3$$/sub$$[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]·3H$$sub$$2$$/sub$$O （5）Cu$$sup$$II$$/sup$$（Bbtz）（H$$sub$$2$$/sub$$Bbi）（H$$sub$$2$$/sub$$Btp）[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]（6）Cu$$sub$$4$$/sub$$$$sup$$I$$/sup$$Bbi$$sub$$4$$/sub$$SiW$$sub$$12$$/sub$$O$$sub$$40$$/sub$$（7）在化合物3到7中，以经典杂多金属氧酸盐Wells-Dawson为次级结构建筑单元，构筑结构新颖的杂化化合物。化合物3到7是在相同体系中合成的，由于引入的有机配体的种类、数量的不同，使5个化合物的结构存在着巨大的差异。化合物3是选用有机胺作为抗衡阳离子，从而得到一个3D超分子化合物。化合物4在化合物3的基础上引入柔性有机配体BBI，使得化合物从超分子结构变成2D层状结构。在化合物4的基础上，我们在体系中加入第二种有机刚性配体，是化合物的维度继续增长，结构也变得更加复杂。基于此想法，我们在合成化合物6的时候我们在体系中同时引入3中有机配体，并且刚性配体跟柔性配体同时参加反应，使得我们得到了含有少量溶剂可进入体积，并且结构及其复杂的3D结构化合物。化合物7只加入刚性有机配体，最后得到了含有螺旋结构的3D化合物。3.以八钼酸盐型多金属氧酸盐为次级结构单元选择有机配体BBTZ以及金属Cu离子，在离子热的条件下合成并表征了3个结构新颖的无机-有机杂化化合物。Cu$$sub$$8$$/sub$$$$sup$$I$$/sup$$BBTZ$$sub$$6$$/sub$$[(-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$)(β-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$)]（8）（Cu$$sup$$I$$/sup$$BBTZ）$$sub$$4$$/sub$$[Mo$$sub$$7$$/sub$$Cu$$sup$$II$$/sup$$O$$sub$$24$$/sub$$（H$$sub$$2$$/sub$$O）$$sub$$2$$/sub$$]·6H$$sub$$2$$/sub$$O （9）Cu$$sup$$II$$/sup$$Cu$$sub$$2$$/sub$$$$sup$$I$$/sup$$BBTZ$$sub$$5$$/sub$$[β-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$]（10）（CuBBTZ$$sub$$2$$/sub$$）2Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$（11）在化合物8到10中，选用同多八钼酸盐为次级结构建筑单元，在离子热的条件下合成了3个结构新奇的化合物。我们调整化合物反应时的反应物摩尔比例跟反应时的pH，调整化合物最后的结构。化合物8跟化合物9具有基本相同的反应初始浓度，我们调整反应的初始摩尔比例，得到了结构截然不同的两个缠结化合物同时我们保持化合物9的反应初始摩尔比例，将反应的初始pH值下降，得到了化合物10。4.以八钼酸盐型同多金属氧酸盐为次级结构建筑单元，以四丁基胺为模板，以Cu$$sup$$II$$/sup$$（BBTZ）2为金属有机桥连，在离子热的条件下合成多金属氧酸盐基金属有机多孔材料，并初步的研究了3个化合物的离子交换跟气体吸附性质。（TBA）2[Cu$$sup$$II$$/sup$$（BBTZ）$$sub$$2$$/sub$$(β-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$)]（12）（TBA）2[Cu$$sup$$II$$/sup$$（BBTZ）$$sub$$2$$/sub$$(α-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$)]（13）（TBA）2[Cu$$sup$$II$$
In this paper, we selected Polyoxometalates as the basic building units with differentkinds of organic ligands and Cu atoms to obtain a series of novel polyoxometalates basedinorganic-organic hybrid materials with excellent natures under the ionthermal conditions,and discuss the pH of the reactions and the different rigid organic ligands influence to thestructure and nature of the compounds, and study the potential applications of compoundscarefully.In this paper13Polyoxometalates based inorganic-organic hybrids have been obtainedunder ionthermal conditions through different reaction condition, different rate of the reactantand different orgniac ligands, and characterizated the structures and the properties of thecompounds through ICP-AES, IR, TG, XPS, XPRD, IP, UV, SEM, MS, NMR, gas adsoption,GC, LC and electrochemical workstation. The photocatalytic activity, ion exchange and gasadsorption were carefully studied.1. Two Super molecule compounds have been abtained and characterizated usingWells-Dawson units as second building block with different solvent.（H$$sub$$2$$/sub$$BBI）$$sub$$3$$/sub$$P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$·H$$sub$$2$$/sub$$O （1）H$$sub$$2$$/sub$$（H$$sub$$2$$/sub$$BBI）$$sub$$2$$/sub$$P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$·2H$$sub$$2$$/sub$$O （2）Using the same reactant and different solvent, two novel Polyoxometalates based Supermolecules have been obtained under the hydrothermal and pound1is a novel3D super molecule structure using water as the solvent. Changing thesolvent to ILs, compound2was crystallizated in P1space group, with the same reactant,resulted a racemation compound. Different solvent different space group came true.2. Five novel Wells-Dawson based hybrids have been synthesized and characterizatedunder the ionothermal condition, using second building units （Wells-Dawson type POMs） anddifferent kinds of flexible organic ligands and Cu cation as the reactant.H$$sub$$3$$/sub$$（Tea）（Bmim）$$sub$$3$$/sub$$[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]·3H$$sub$$2$$/sub$$O （3）Cu$$sup$$II$$/sup$$（Bbi）$$sub$$1.5$$/sub$$（H$$sub$$2$$/sub$$Bbi）$$sub$$2$$/sub$$[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]（4）Cu$$sup$$II$$/sup$$2.5（Mimin）（HMimin）（Bbi）3[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]·3H$$sub$$2$$/sub$$O （5）Cu$$sup$$II$$/sup$$（Bbtz）（H$$sub$$2$$/sub$$Bbi）（H$$sub$$2$$/sub$$Btp）[P$$sub$$2$$/sub$$W$$sub$$18$$/sub$$O$$sub$$62$$/sub$$]（6）Cu$$sub$$4$$/sub$$$$sup$$I$$/sup$$Bbi$$sub$$4$$/sub$$SiW$$sub$$12$$/sub$$O$$sub$$40$$/sub$$（7）In compound3to7, the five novel compounds ere obtained using classic Wells-Dawsonas second building block. They were obtained under the same reaction condition, and becauseof introducing the different kinds of organic ligands, the structures of the5compounds werefar more different from each other. In3, organic amine were using as the counter caution, andresulted a novel3D super molecule structure. In4, introducing flexible organic ligand BBI, itmake the structure of compound4from super molecue to2D layer framework. After that,another rigid organic ligand were introduced in to the reaction system,3D framework withcomplicated topology were obtained. Based on this, to shnthesize compound6, three kinds oforganic ligands were introduced in to the reactant, and then resulted a3D framework of compound6with24%solvent accessible volume and complicated topology. However incompound7, there is only one kind of organic ligand, in the end a novel3D compound withscrew was obtained.3. Three novel isopolymolybdate based inorganic-organic hybrid heve been synthesizedand characterizated under the ionothermal condition, using isopolymolybdate as the secondbuilding block, and coordinated with Cu cations and the organic ligand BBTZ.Cu$$sub$$8$$/sub$$$$sup$$I$$/sup$$BBTZ$$sub$$6$$/sub$$[(-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$)(-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$)]（8）（Cu$$sup$$I$$/sup$$BBTZ）$$sub$$4$$/sub$$[Mo$$sub$$7$$/sub$$Cu$$sup$$II$$/sup$$O24（H$$sub$$2$$/sub$$O）$$sub$$2$$/sub$$]·6H$$sub$$2$$/sub$$O （9）Cu$$sup$$II$$/sup$$Cu$$sup$$I$$/sup$$2BBTZ5[-Mo$$sub$$8$$/sub$$O$$sub$$26$$/sub$$]（10）（CuBB
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