基于杂多钨、钼酸盐的有机—无机杂化化合物及混合型铌配合物的合成、结构与性能
|
摘要
本论文选用杂多钨、钼酸盐为无机建筑块，选择不同的有机含氮多齿配体和金属离子，构筑了一系列新颖的有机无机杂化化合物。探讨了各种不同反应条件对产物晶体结构的影响规律，并探索合成的新物质的结构与其性能间的关系。利用水热条件下合成的技术，通过调节反应的各种条件和反应的不同原料等，合成了12种基于多金属钨、钼酸盐的有机无机杂化化合物及混合性铌配合物。通过元素分析、红外光谱、热重分析、X-射线粉末衍射，光电子能谱和X-射线单晶衍射等手段对得到的这些晶体的结构进行了表征，并且对这些化合物的电化学、荧光性质进行了初步研究。
1.以Keggin型钨酸盐作为无机建筑块，选择不同有机胺多齿配体和配位模式丰富的d~(10)金属Zn~Ⅱ和Cd~Ⅱ阳离子，在水热反应条件下合成并表征了6个新的有机无机杂化化合物：[Zn(phen)_2]_2(PWVIV11WO_(40))(1)K[Zn(phen)_2(H_2O)]_2(OH)(SiW_(12)O_(40))·H_2O(2)[Zn (bipy)_2(H_2O)]_2(SiW_(12)O_(40))·H_2O (3)[Zn_2(H_2biim)_5](SiW_(12)O_(40))·2H_2O (4)[Cd (phen)_2]_2(SiW_(12)O_(40))(5)[Cd (bipy)_2]_2(SiW_(12)O_(40))(6)phen=1,10-phenaanthrolinebipy=2,2’-bipyridineH_2biim=2,2’-biimidazole
化合物1-3的基本结构单元都是锌的配合物双支撑的Keggin型多金属钨酸盐。化合物1是一种杂多蓝化合物，其结构中的双支撑多金属钨酸盐，通过相邻的邻菲罗啉配体之间的π…π堆积作用形成三维超分子结构。化合物2中相邻的两个双支撑keggin型多酸簇通过K~+离子的桥接形成一维无限链结构。化合物3的结构相似于化合物1。化合物4是由一个Keggin型[SiW_(12)]多阴离子和一个二核[Zn_2(H_2biim)_5]4簇构成的超分子化合物。
化合物5是Cd的配合物双支撑的Keggin型杂多钨酸盐，而化合物6是Cd的配合物四支撑的Keggin型杂多钨酸盐。据我们所知，Cd的配合物双支撑的和四支撑的Keggin型杂多钨酸盐到现在为止未见文献报道。另一方面，d~(10)金属Zn和Cd不仅具有配位模式丰富的特点,而且具有优良的发光性能。研究结果表明化合物1-6都有荧光性质。2无机建筑块，合成了两个未见文献报道的有机-无机杂化化合物,做了荧光性质的初步研究:[Cu_2(H_2biim)_2(μ2-OH)_2]_2[SiW_(12)O_(40)](7)[Cu(H_2biim)_2(OH)][Cu(H_2biim)_2]{Cu(H_2biim)_2[BW_(12)O_(40)]}·3H_2O (8)
化合物7由Cu二聚体[Cu_2(H_2biim)_2(μ2-OH)+2]_2和Keggin型多阴离[SiW412O_(40)]-构成的四支撑二维结构的化合物。在二聚体片段中，两个Cu间的距离为2.588，铜之间存在着较强的金属-金属作用，这可能是化合物7具有荧光发射的主要原因。化合物8的结构中存在晶体学上独立的三种Cu-H_2biim配合物片段,通过两种不同的π…π堆积作用形成该化合物的三维超分子结构。
3.以[P_4Mo_6]型或Keggin型多金属钼酸盐作为无机建筑块，选择不同的有机胺多齿配体和金属阳离子，在水热条件下合成并表征了3个新型的有机无机杂化化合物：(H_2en)4(en)_2{Na0.5[Mo_6O_(15)(HPO_4)(H_2PO_4)3]}{Na0.5[Na2(H_2O)_5Mo_6O_(15)(PO_4)(HPO_4)(H_2PO_4)_2]}·10H_2O (9)(H.2en)12K2(H_2O)_2Na[H19K(P_4Mo_6O_(31))_2]_26H_2O (10)[Cu(2,2’-bipy)]6[(PMoVIV11MoO_(40))][(Mo6O22)].H_2O (11)
化合物9和10是以M[P_4Mo_6O_(31)]_2(M＝Na,K)二聚体为基本单元的化合物。化合物9的基本结构单元为Na[Mo6P4]_2二聚体，每个二聚体与相邻的四个{NaO6}八面体相连形成带有孔道的一维链。化合物10是Na和K混合金属桥的单元结构M[P_4Mo_6O_(31)]_2构成的。最值得一提的是在化合物10的二维结构中存在着两种类型的一维隧道。
化合物11是[Mo8-6O22]同多阴离子和[PMoVI
11MoVO_(40)]4-杂多阴离子簇通过[Cu(2,2’-bipy)]_2+配合物以交叉的形式链接延伸形成一维长链的化合物。这个化合物{Mo6}-Cu-{PMo12}长链中存在的{Mo6}簇是很罕见的结构单元。
4.使用氢氟酸溶解Nb2O5的方法，在铜离子和有机含氮配体邻菲罗啉的存在下，经过水热反应成功合成了一个新型铌－铜混合配合物：[Cu_2(phen)4(NbF_4)_2(μ-O)_2(μ-F)][NbF_6]（12）
化合物12中两个Cu(C_(12)H_8N_2)_2O和两个NbOF_5配合物基团通过O、F原子桥连而构筑的。这种F原子起桥连作用的情况是很少见的。该化合物具有荧光，热稳定性高，而且难溶于水。因此化合物12可能是一个潜在的固体荧光发射材料。
In this thesis, a series of organic-inorganic hybrid materials with interestingarchitectures have been obtained by the assembly of polyoxotungstates orpolyoxomolybdates, different organic ligands and metal cations. We have investigatedthat the reaction conditions, could affect the structure of the products. Further, someproperties of the compounds have been investigated, and the relationships betweenstructures and property for these new compounds are studied.Herein, Twelve Polyoxotungstates or Polyoxomolybdates based organic-inorganichybrids and Niobium Mixed Complex have been synthesized byhydrothermalsynthesis methods. These compounds have been structurally characterized byelemental analyses, IR, TG, XRPD and single crystal X-ray diffractions. Further,electrochemical and photoluminescence properties have been studied.
1. Ten new orgainic-inorganic hybrid compounds based on KegginPolyoxotungstates, organic ligands and d~(10)metals Zn_2+or Cd2+cations have beensynthesized under hydrothermal conditions:[Zn(phen)_2]_2(PWVI11WVO_(40))(1)K[Zn(phen)_2(H_2O)]_2(OH)(SiW_(12)O_(40))·H_2O (2)[Zn (bipy)_2(H_2O)]_2(SiW_(12)O_(40))·H_2O (3)[Zn_2(H_2biim)_5](SiW_(12)O_(40))·2H_2O (4)[Cd (phen)_2]_2(SiW_(12)O_(40))(5)[Cd (bipy)_2]_2(SiW_(12)O_(40))(6)phen=1,10-phenaanthrolinebipy=2,2’-bipyridineH_2biim=2,2’-biimidazole
In compounds1-3, the basic structural unit is the same, that is, Zn(II) complexesare linked by the bi-supporting Keggin clusters. Compound1isa heteropoly blue, which is a three-dimensional supramolecular structure formed bythe π π stacking interactions between bi-supporting polytungstates. Compound2is aone-dimensional chain formed by K~+ions bridging two adjacentbi-supporting Keggin clusters. The structure of compound3is similar to that ofcompound1. Compound4is a supramolecular compound composed ofKeggin type [SiW_(12)] anions and dinuclear [Zn_2(H_2biim)_5]4+clusters.
Compound5is a bisupporting Keggin-type polyoxotungstate linked to Cd complex, while compound6is a tetra-supporting Keggin cluster linked to Cdcomplex. As far as we know, no compounds relating toKeggin-type polyoxotungstates linked to two or four Cd complexes have beenreported in the literature. On the other hand, the d~(10)metal, like Zn and Cd, not onlypossesses variable coordination modes, but also has excellent luminescenceproperties. The results show that compounds1-6have relativelystrong fluorescence properties.
2. Two hybrid compounds based on the Keggin Polyoxotungstates,2,2’-biimidazole ligand and Copper cations have been obtained under hydrothermalconditions:[Cu_2(H_2biim)_2(μ2-OH)_2]_2[SiW_(12)O_(40)](7)[Cu(H_2biim)_2(OH)][Cu(H_2biim)_2]{Cu(H_2biim)_2[BW_(12)O_(40)]}·3H_2O (8)
Compound7is a two-dimensional layer constructed by twodimers [Cu_2(H_2biim)_2(μ2-OH)_2]_2+and Keggin-type anionic clusters [SiW_(12)O_(40)]~4-. Inthe dimer, the distance between of two Cu(II) is2.588, suggesting thestrong metal metal effects. In addition, relatively strong fluorescence emission canbe found for compound7. In compound8, there are three kinds of crystallographicunique Cu(II) ions. The three-dimensional supramolecular structure of8is formedby two different π π interactions among three kinds of Cu-H_2biim complexes.
3. The [P_4Mo_6] or keggin type polyoxomolybdates has been chosen as inorganicbuilding blocks, and three compounds have been obtained under hydrothermalcondition:(H_2en)4(en)_2{Na0.5[Mo_6O_(15)(HPO_4)(H_2PO_4)3]}{Na0.5[Na2(H_2O)_5Mo_6O_(15)(PO_4)(HPO_4)(H_2PO_4)_2]}·10H_2O (9)(H_2en)12K2(H_2O)_2Na [H19K(P_4Mo_6O_(31))_2]_2·6H_2O (10)[Cu(2,2’-bipy)]6[(PMoVI11MoVO_(40))][(Mo6O22)]·H_2O (11)
Both compounds9and10are composed of M[P_4Mo_6O_(31)]_2(M=K or Na)dimmers. In the basic structural unit of compound9, there are two Na[Mo6P4]_2dimers, each dimer and four adjacent {NaO6} are connected to forma one-dimensional chain. In compound10, both Na and K cobridge the dimer[Mo6P4]_2.
It should be noted that there are two types of1D channels in compound10.
Compound11is a1D chain composed of [Mo_8-6O_(22)]anion and[PMoVI11MoVO_(40)]4-anion clusters linked by [Cu(2,2'-bipy)]_2+complexes. The{Mo6} cluster in the1D long chain {Mo_6}-Ｃu-{PMo_(12)} is very rare.
4. A novel niobium-transition metal mixed complexes with1,10-phenanthrolinehas been synthesized:[Cu_2(phen)4(NbF_4)_2(μ-O)_2(μ-F)][NbF_6](12)
Compound12is composed of two Cu(C_(12)H_8N_2)_2O and two NbOF5complexesbridged by O and F atoms. The F atoms play a bridging role, which is rare. Thecompound is difficult to dissolve in water, and has relatively strong fluorescence, highthermal stability. Therefore, compound12could be a potentialsolid fluorescence emission material.
1.以Keggin型钨酸盐作为无机建筑块，选择不同有机胺多齿配体和配位模式丰富的d~(10)金属Zn~Ⅱ和Cd~Ⅱ阳离子，在水热反应条件下合成并表征了6个新的有机无机杂化化合物：[Zn(phen)_2]_2(PWVIV11WO_(40))(1)K[Zn(phen)_2(H_2O)]_2(OH)(SiW_(12)O_(40))·H_2O(2)[Zn (bipy)_2(H_2O)]_2(SiW_(12)O_(40))·H_2O (3)[Zn_2(H_2biim)_5](SiW_(12)O_(40))·2H_2O (4)[Cd (phen)_2]_2(SiW_(12)O_(40))(5)[Cd (bipy)_2]_2(SiW_(12)O_(40))(6)phen=1,10-phenaanthrolinebipy=2,2’-bipyridineH_2biim=2,2’-biimidazole
化合物1-3的基本结构单元都是锌的配合物双支撑的Keggin型多金属钨酸盐。化合物1是一种杂多蓝化合物，其结构中的双支撑多金属钨酸盐，通过相邻的邻菲罗啉配体之间的π…π堆积作用形成三维超分子结构。化合物2中相邻的两个双支撑keggin型多酸簇通过K~+离子的桥接形成一维无限链结构。化合物3的结构相似于化合物1。化合物4是由一个Keggin型[SiW_(12)]多阴离子和一个二核[Zn_2(H_2biim)_5]4簇构成的超分子化合物。
化合物5是Cd的配合物双支撑的Keggin型杂多钨酸盐，而化合物6是Cd的配合物四支撑的Keggin型杂多钨酸盐。据我们所知，Cd的配合物双支撑的和四支撑的Keggin型杂多钨酸盐到现在为止未见文献报道。另一方面，d~(10)金属Zn和Cd不仅具有配位模式丰富的特点,而且具有优良的发光性能。研究结果表明化合物1-6都有荧光性质。2无机建筑块，合成了两个未见文献报道的有机-无机杂化化合物,做了荧光性质的初步研究:[Cu_2(H_2biim)_2(μ2-OH)_2]_2[SiW_(12)O_(40)](7)[Cu(H_2biim)_2(OH)][Cu(H_2biim)_2]{Cu(H_2biim)_2[BW_(12)O_(40)]}·3H_2O (8)
化合物7由Cu二聚体[Cu_2(H_2biim)_2(μ2-OH)+2]_2和Keggin型多阴离[SiW412O_(40)]-构成的四支撑二维结构的化合物。在二聚体片段中，两个Cu间的距离为2.588，铜之间存在着较强的金属-金属作用，这可能是化合物7具有荧光发射的主要原因。化合物8的结构中存在晶体学上独立的三种Cu-H_2biim配合物片段,通过两种不同的π…π堆积作用形成该化合物的三维超分子结构。
3.以[P_4Mo_6]型或Keggin型多金属钼酸盐作为无机建筑块，选择不同的有机胺多齿配体和金属阳离子，在水热条件下合成并表征了3个新型的有机无机杂化化合物：(H_2en)4(en)_2{Na0.5[Mo_6O_(15)(HPO_4)(H_2PO_4)3]}{Na0.5[Na2(H_2O)_5Mo_6O_(15)(PO_4)(HPO_4)(H_2PO_4)_2]}·10H_2O (9)(H.2en)12K2(H_2O)_2Na[H19K(P_4Mo_6O_(31))_2]_26H_2O (10)[Cu(2,2’-bipy)]6[(PMoVIV11MoO_(40))][(Mo6O22)].H_2O (11)
化合物9和10是以M[P_4Mo_6O_(31)]_2(M＝Na,K)二聚体为基本单元的化合物。化合物9的基本结构单元为Na[Mo6P4]_2二聚体，每个二聚体与相邻的四个{NaO6}八面体相连形成带有孔道的一维链。化合物10是Na和K混合金属桥的单元结构M[P_4Mo_6O_(31)]_2构成的。最值得一提的是在化合物10的二维结构中存在着两种类型的一维隧道。
化合物11是[Mo8-6O22]同多阴离子和[PMoVI
11MoVO_(40)]4-杂多阴离子簇通过[Cu(2,2’-bipy)]_2+配合物以交叉的形式链接延伸形成一维长链的化合物。这个化合物{Mo6}-Cu-{PMo12}长链中存在的{Mo6}簇是很罕见的结构单元。
4.使用氢氟酸溶解Nb2O5的方法，在铜离子和有机含氮配体邻菲罗啉的存在下，经过水热反应成功合成了一个新型铌－铜混合配合物：[Cu_2(phen)4(NbF_4)_2(μ-O)_2(μ-F)][NbF_6]（12）
化合物12中两个Cu(C_(12)H_8N_2)_2O和两个NbOF_5配合物基团通过O、F原子桥连而构筑的。这种F原子起桥连作用的情况是很少见的。该化合物具有荧光，热稳定性高，而且难溶于水。因此化合物12可能是一个潜在的固体荧光发射材料。
In this thesis, a series of organic-inorganic hybrid materials with interestingarchitectures have been obtained by the assembly of polyoxotungstates orpolyoxomolybdates, different organic ligands and metal cations. We have investigatedthat the reaction conditions, could affect the structure of the products. Further, someproperties of the compounds have been investigated, and the relationships betweenstructures and property for these new compounds are studied.Herein, Twelve Polyoxotungstates or Polyoxomolybdates based organic-inorganichybrids and Niobium Mixed Complex have been synthesized byhydrothermalsynthesis methods. These compounds have been structurally characterized byelemental analyses, IR, TG, XRPD and single crystal X-ray diffractions. Further,electrochemical and photoluminescence properties have been studied.
1. Ten new orgainic-inorganic hybrid compounds based on KegginPolyoxotungstates, organic ligands and d~(10)metals Zn_2+or Cd2+cations have beensynthesized under hydrothermal conditions:[Zn(phen)_2]_2(PWVI11WVO_(40))(1)K[Zn(phen)_2(H_2O)]_2(OH)(SiW_(12)O_(40))·H_2O (2)[Zn (bipy)_2(H_2O)]_2(SiW_(12)O_(40))·H_2O (3)[Zn_2(H_2biim)_5](SiW_(12)O_(40))·2H_2O (4)[Cd (phen)_2]_2(SiW_(12)O_(40))(5)[Cd (bipy)_2]_2(SiW_(12)O_(40))(6)phen=1,10-phenaanthrolinebipy=2,2’-bipyridineH_2biim=2,2’-biimidazole
In compounds1-3, the basic structural unit is the same, that is, Zn(II) complexesare linked by the bi-supporting Keggin clusters. Compound1isa heteropoly blue, which is a three-dimensional supramolecular structure formed bythe π π stacking interactions between bi-supporting polytungstates. Compound2is aone-dimensional chain formed by K~+ions bridging two adjacentbi-supporting Keggin clusters. The structure of compound3is similar to that ofcompound1. Compound4is a supramolecular compound composed ofKeggin type [SiW_(12)] anions and dinuclear [Zn_2(H_2biim)_5]4+clusters.
Compound5is a bisupporting Keggin-type polyoxotungstate linked to Cd complex, while compound6is a tetra-supporting Keggin cluster linked to Cdcomplex. As far as we know, no compounds relating toKeggin-type polyoxotungstates linked to two or four Cd complexes have beenreported in the literature. On the other hand, the d~(10)metal, like Zn and Cd, not onlypossesses variable coordination modes, but also has excellent luminescenceproperties. The results show that compounds1-6have relativelystrong fluorescence properties.
2. Two hybrid compounds based on the Keggin Polyoxotungstates,2,2’-biimidazole ligand and Copper cations have been obtained under hydrothermalconditions:[Cu_2(H_2biim)_2(μ2-OH)_2]_2[SiW_(12)O_(40)](7)[Cu(H_2biim)_2(OH)][Cu(H_2biim)_2]{Cu(H_2biim)_2[BW_(12)O_(40)]}·3H_2O (8)
Compound7is a two-dimensional layer constructed by twodimers [Cu_2(H_2biim)_2(μ2-OH)_2]_2+and Keggin-type anionic clusters [SiW_(12)O_(40)]~4-. Inthe dimer, the distance between of two Cu(II) is2.588, suggesting thestrong metal metal effects. In addition, relatively strong fluorescence emission canbe found for compound7. In compound8, there are three kinds of crystallographicunique Cu(II) ions. The three-dimensional supramolecular structure of8is formedby two different π π interactions among three kinds of Cu-H_2biim complexes.
3. The [P_4Mo_6] or keggin type polyoxomolybdates has been chosen as inorganicbuilding blocks, and three compounds have been obtained under hydrothermalcondition:(H_2en)4(en)_2{Na0.5[Mo_6O_(15)(HPO_4)(H_2PO_4)3]}{Na0.5[Na2(H_2O)_5Mo_6O_(15)(PO_4)(HPO_4)(H_2PO_4)_2]}·10H_2O (9)(H_2en)12K2(H_2O)_2Na [H19K(P_4Mo_6O_(31))_2]_2·6H_2O (10)[Cu(2,2’-bipy)]6[(PMoVI11MoVO_(40))][(Mo6O22)]·H_2O (11)
Both compounds9and10are composed of M[P_4Mo_6O_(31)]_2(M=K or Na)dimmers. In the basic structural unit of compound9, there are two Na[Mo6P4]_2dimers, each dimer and four adjacent {NaO6} are connected to forma one-dimensional chain. In compound10, both Na and K cobridge the dimer[Mo6P4]_2.
It should be noted that there are two types of1D channels in compound10.
Compound11is a1D chain composed of [Mo_8-6O_(22)]anion and[PMoVI11MoVO_(40)]4-anion clusters linked by [Cu(2,2'-bipy)]_2+complexes. The{Mo6} cluster in the1D long chain {Mo_6}-Ｃu-{PMo_(12)} is very rare.
4. A novel niobium-transition metal mixed complexes with1,10-phenanthrolinehas been synthesized:[Cu_2(phen)4(NbF_4)_2(μ-O)_2(μ-F)][NbF_6](12)
Compound12is composed of two Cu(C_(12)H_8N_2)_2O and two NbOF5complexesbridged by O and F atoms. The F atoms play a bridging role, which is rare. Thecompound is difficult to dissolve in water, and has relatively strong fluorescence, highthermal stability. Therefore, compound12could be a potentialsolid fluorescence emission material.
引文
[1] Pope M T. Heteropoly and Isopoly Oxometalates [M]. Springer-Verlag: Berlin,1983,1-10.
[2]王恩波，李阳光，鹿颖等，多酸化学概论[M]，长春：东北师范大学出版社，2007,4.
[3] Hu J K, Yu X Y, Luo Y H, et al. Hydrothermal syntheses and crystal structures of two novel Inorganic–organic hybrid compounds based on saturated α-Keggin phosphomolybdate clusters [J]. Inorg ChemComm,2013,32,37–41.
[4] Yuji Kikukawa, Kosuke Suzuki, Noritaka Mizuno, et al. Synthesis, Structure Characterization, andReversible Transformation of a Cobalt Salt of a Dilacunary γ Keggin Silicotungstate and Sandwich-TypeDi-and Tetracobalt-Containing Silicotungstate Dimers [J]. Inorg Chem.2013,52,86448652.
[6] Duan H, Zhang Z M, Wang E B, et al. Sandwich-type tungstoantimonates decorated by theheterometallic3d–5p clusters[J]. Inorg Chem Comm,2013,33,90–94.
[7] Yin P C, Li T, Long D L, et al. Exploring the Programmable Assembly of a Polyoxometalate OrganicHybrid via Metal Ion Coordination[J]. J Am Chem Soc,2013,135,1342513432.
[8] Kazuhiro Uehara, Takamichi Oishi, Noritaka Mizuno, et al. Synthesis and Characterization ofMolecular Hexagons and Rhomboids and Subsequent Encapsulation of Keggin-Type Polyoxometalates byMolecular Hexagons [J]. Inorg Chem.2013,52,1120011209.
[9] Shi Z Y, Peng J, Li Y G, et al. Assembly of multinuclear Ag complexes and Keggin polyoxometalatesadjusted by organic ligands:syntheses, structures and luminescence [J]. CrystEngComm,2013,15,7583–7588.
[10] Wu N, Qin Y, Wang E B, et al. Two layered copper–bis(triazole) assemblieswith Kegginpolyoxoanions as pendants: Syntheses, structures and photocatalytic properties [J]. Inorg Chem Comm,2013,37,174–177.
[11] Pedro I. Molina, Haralampos N. Miras, Leroy Cronin, et al. Exploring the Assembly ofSupramolecular Polyoxometalate Triangular Morphologies with Johnson Solid Cores:[(MnII(H2O)3)2(K{α-GeWII1910Mn2O38}3)][J]. Inorg. Chem.2013,52,92849289.
[12] Cui K Y, Li F Y, Xu L, et al. A3D all-inorganic architecture based on the [H2W112O42]0-building blockwith different alkalineearth metal linkers: crystal structures, surface photovoltage and photoluminescentproperties [J]. CrystEngComm,2013,15,4721–4729.
[13] Wang X, Zhang M M, Hao X L et al. Polyoxometalate-Induced New Self-Assemblies Based onCopper Ions and Bichelate-Bridging Ligands [J]. Cryst. Growth Des.2013,13,34543462.
[14] Raju Mekala, Sabbani Supriya, and Samar K. Das. Fate of a Giant {Mo72Fe30} Type PolyoxometalateCluster in an Aqueous Solution at Higher Temperature: Understanding Related Keplerate Chemistry, fromMolecule to Material[J]. Inorg. Chem.2013,52,97089710.
[15] Maxim N. Sokolov, Sergey A. Adonin, Dmitry A. Mainichev, et al. New {RuNO} Polyoxometalate
[PWI11O39RuI(NO)]4: Synthesis and Reactivity [J]. Inorg. Chem.2013,52,96759682.
[16] Yang L, Ma P T, Wang J P, et al. A Crown-Shaped24-Molybdate Cluster Constructed byOrganotriphosphonate Ligand [J]. Inorg. Chem.2013,52,82858287.
[17] Shi Z Y, Peng J, Yu X, et al. A new3D Keggin-POM based metal–organic framework of Cu andH2biim: Assembly and properties of fluorescence and electrochemistry [J]. Inorg Chem Comm,2013,28,85–89.
[18] Sayaka Uchida, Eri Takahashi, and Noritaka Mizuno. Porous Ionic Crystals Modified byPost-Synthesis of K2[Cr3O(OOCH)6(etpy)3]2[α-SiW12O40]·8H2O through Single-Crystal-to-Single-CrystalTransformation [J]. Inorg. Chem.2013,52,93209326.
[19] Cao G J,Rong C.(C6H6)4[H4GeMo12O40].1.5H2O: A New Polyoxomolybdate Obtained from In SituReaction [J]. J Clust Sci,2013,24,843–850.
[20] Wang X, Peng J, K Alimaje, et al. Two Keggin polyoxoanion-based hybrids composed of CuI/tbzsegments:Syntheses, structures and electrochemical properties [J]. Inorg Chem Comm,2013,36,141–145.
[21] Zhao J W, Shi D Y, Chen L J, et al. Tetrahedral Polyoxometalate Nanoclusters with TetramericRare-Earth Cores and Germanotungstate Vertexes [J]. Cryst. Growth Des.2013,13,43684377.
[22] Shi Z Y, Peng J, Zhang Z Y, et al.et al. Syntheses, structures and photoluminescence of twoDawson-based hybrid materials with polynuclear silver clusters [J]. Inorg Chem Comm,2013,33,105–108.
[23] Liu Z J,Yao S, Wang E B,et al. A polyoxometalate-based ionic crystal assembly from a heterometalliccluster and polyoxoanions with visiblelight catalytic activity [J].RSC Adv.,2013,3,20829.
[24] Amaia Iturrospe, Benat Artetxe, Santiago Reinoso,et al. Copper(II) Complexes of Tetradentate PyridylLigands Supported on Keggin Polyoxometalates: Single-Crystal to Single-Crystal TransformationsPromoted by Reversible Dehydration Processes [J]. Inorg. Chem.2013,52,30843093.
[25] Guo D, Teng S Y, Liu Z G,et al. Synthesis and Structure of [Co14-2Bi2(a or b-B-CoW9O34)2]Isomersand Their Catalytic Water Oxidation [J]. J Clust Sci,2013,24,549–558.
[26] Masooma Ibrahim, Xiang Y X, Ulrich Kortz,et al. Synthesis, Magnetism, and Electrochemistry of theNi14-and Ni5Containing Heteropolytungstates[Ni14(OH)6(H2O)10(HPO4)4(P2W15O56)4]34and
[Ni5(OH)4(H2O)4(β-GeW9O34)(β-GeW8O30(OH))]13[J]. Inorg. Chem.2013,52,83998408.
[27] Wang Y C, Li F Y, Xu L, et al. Multidimensional crystal frameworks based onHeteropoly bluebuilding block of [SiW610MoV2O40]:synthesis, structures and magnetic properties [J].Dalton Trans.,2013,42,5839.
[28] Li J S, Sang X J, Chen W L,et al. The research of a new polyoxometalates based photosensitizer ondye sensitized solar cell [J]. Inorg Chem Comm,2013,38,78–82.
[29] Zhang J, Chen W L, WangE B,et al. Synthesis and catalytic properties of novel POM@TiO2composite materials [J]. Inorg Chem Comm,2013,38,96–99.
[30] Zhang C H, Chen Y G, Liu S X,et al. Weakley sandwich-type anion in organic–inorganic hybridcompound with3D framework [J]. Inorg Chem Comm,2013,29,45–48.
[31] Cassan-Pastor N，Baker L C W. Magnetic properties of mixed-valence heteropoly blues interactionswith complexes containjing paramagnetic atoms in obvious sites as well as ‘blue’electrodes delocalizedover polytungstate frameworks[J]．J Am Chem Soc，1992，114(26)，10384—10389．
[32] Zheng X P, Lu Y, Wang E B,et al. Two new metal–organic frameworks based on cyclicdodecanuclear copper units[J]. Inorg Chem Comm,2013,33,29–32.
[33] Li X M, Chen Y G, Su C N,et al. Functionalized Pentamolybdodiphosphate-Based Inorganic-OrganicHybrids: Synthesis, Structure, and Properties [J].Inorg. Chem.2013,52,1142211427.
[34] Shen J Q, Yao S, Zhang Z M,et al. Self-assembly and photocatalytic property ofgermanoniobate [H6Ge4Nb16O56]10: encapsulating four {GeO4} tetrahedra within a {Nb16} cage[J].DaltonTrans.,2013,42,5812.
[35] Liu D, Lu, Wang E B,et al. Polyoxometalate-based purely inorganic porous frameworks with selectiveadsorption and oxidative catalysis functionalities [J].Chem. Commun.,2013,49,3673.
[36] Wu H H, Yao S, Zhang Z M,et al. Heterometallic appended {MMnIII4} cubanes encapsulated bylacunary polytungstate ligands [J]. Dalton Trans.,2013,42,342.
[37] Han Q X, He C, Niu J Y,et al. Engineering Chiral Polyoxometalate Hybrid Metal OrganicFrameworks for Asymmetric Dihydroxylation of Olefins [J]. J. Am. Chem. Soc.2013,135,1018610189
[38] Toshihiro Y．Photo and Electrochromism of PolyoxometalaIes and Pelaled Material[J]．Chem Rev，1998．98：307-325.
[39]王恩波，胡长文，许林等，多酸化学导论[M]，北京：化学工业出版社，1997，14-47.
[40] M. I. Khan, S. Cevik, R. Hayashi,“First12-tungstovanadate Keggin compound:synthesis and crystalstructure of [Me4N]7[VW12O40]·15H2O.” J.Chem. Soc., Dalton Trans1999,1651-1654.
[41] A. Yokoyama, T. Kojima, K. Ohkubo, S. Fukuzumi,“A discrete conglomerate of a distortedMo(V)-porphyrin with a directly coordinated keggin-type polyoxometalate”, Chem. Commun.,2007,3997-3999.
[42] Y. Xu, J.Q. Xu, K.L. Zhang, Y. Zhang, X.Z. You,“Keggin unit supported transition metal complexes:hydrothermal synthesis and characterization of[Ni(2,2’-bipy)3]1.5[PW12O40Ni(2,2’-bipy)2(H2O)]·0.5H2Oand [Co(1,10’-phen)3]1.5[PMo12O40Co(1,10’-phen)2(H2O)]·0.5H2O”, Chem. Commun.2000,153-154.
[43] J.P. Wang, Q. Ren, J.W. Zhao, J.Y. Niu,“A novel Keggin-type tungstogermanate dimer bearingdinuclear copper-organic coordination ions:{H8[Cu(phen)(μ2-CH3COO)2Cu(phen)(H2O)]2[Ge2W23CuO80]}·24H2O”,Inorganic Chemistry Communications2006,9,1281-1285.
[44] Inman C, Knaust J M, Keller S W. A polyoxometallate-templated coordination polymer: synthesis andcrystal structure of [Cu3(4,4’-bipy)5(MeCN)2]PW12O40·2C6H5CN [J]. J Chem Soc, Chem Commun,2002,156-157.
[45] Knaust J M, Inman C, Keller S W. A host-guest complex between a metal-organic cyclotriveratryleneanalog and a polyoxometalate:[Cu6(4,7-phenanthroline)8(MeCN)4]2PM12O40(M=Mo or W)[J]. ChemCommun,2004,492-493.
[46] Kong X J, Ren Y P, Zheng P Q, et al. Construction of Polyoxometalates-Based CoordinationPolymersthrough Direct Incorporation between Polyoxometalates and the Voids in a2D Network [J]. InorgChem,2006,45(26):10702-10711.
[47] Meng F X, Chen Y G, Liu H B, Assembly of two novel coordination polymers constructedfrommetal-organic framework and Keggin-template [J]. J Mole Struct,2007,837:224-230
[48] E. Burkholder, V. Golub, C.J. O’Connor, J. Zubieta,“Hydrothermal synthesis f a one-dimensionalbimetallic mixed valence oxide [{Cu4(terpy)4(PO4)(H2O)2}{WVI10WV2O36(PO4)}]·5H2O, a materialconstructed from{PW5-12O40}and novel [{Cu4(terpy)4(PO5+4)(H2O)2}cluster building blocks”,Inorg. Chem.Commun.,2004,7,363-366.
[49] S. Chang, C. Qin, E.B. Wang, Y.G. Li, X.L. Wang,“New potassiumion-bridged chainlike assemblyfrom bisupporting Keggin units: K[M(phen)2(H2O)]2[PW12O40]·2H2O (M=Fe, Cu)”, Inorganic ChemistryCommunications2006,9,727-731.
[50] H. Jin, C. Qin, Y.G. Li, E.B. Wang,“[Cu5Cl(4,4’-bipy)5][SiW12O40]1.5H2O:A novel three-dimensionalframework constructed from polyoxometalate clusters and trinuclear Cu(I) complex”, Inorganic ChemistryCommunications2006,9,482-485.
[51] J.Q. Sha, J. Peng, H.S. Liu, B. Xue, J. Chen, A.X Tian, B.X. Dong, P.P. Zhang,“Controlled assemblyof two novel3D hexad-supporting Keggin-polyoxometalate derivatives:{[Cu(4,4’-bipy)]3[HnXW12O40]}
[4,4’-bipy]·2H2O (X=P, n=0; X=Si, n=1)”, Journal of MolecularStructure2007,871,85-91.
[52] J.X. Chen, T.Y. Lan, Y.B. Huang, C.X.Wei, Z.S. Li, Z.C. Zhang,“Hydrothermal synthesis, crystalstructure and properties of a3D-framework polyoxometalate assembly:[Ag(4,4’-bipy)](OH){[Ag(4,4’-bipy)]2[PAgW12O40]}·3.5H2O”, Journal of Solid State Chemistry2006,179,1904-1910
[53] S. Reinoso, P. Vitoria, J. M. Gutiérrez-Zorrilla, L. Lezama, LS. Felices, J.I.Beitia,“Inorganic-Metalorganic Hybrids Based on Copper(II)-Monosubstituted Keggin Polyanions and DinuclearCopper(II)-Oxalate Complexes. Synthesis, X-ray Structural Characterization, and Magnetic Properties”Inorg. Chem.,2005,44,9731-9742.
[54] Fan L L, Xiao D R, Wang E B, et al. An Unprecedented Fivefold Interpenetrating Network Based onPolyoxometalate Building Blocks [J]. Cryst Growth&Des,2007,7(4):592-594.
[55] Bassil B S, Dickman M H, Kammer B, et al. The Monolanthanide-ContainingSilicotungstates[Ln(β12-SiW11O39)2]3-(Ln=La, Ce, Sm, Eu, Gd, Tb, Yb, Lu): A Synthetic and StructuralInvestigation [J].Inorg. Chem.2007,46(7):2452-2458
[56] Jiang C J, Lesbani A, Kawamoto R, et al. Channel-Selective Independent Sorption and Collection ofHydrophilic and Hydrophobic Molecules by Cs2[Cr3O(OOCC2H5)6(H2O)3]2[α-SiW12O40] Ionic Crystal [J].JAm Chem Soc,2006,128(44):14240-14241
[57] Streb C, Ritchie C, Long D L, et al. Modular Assembly of a Functional Polyoxometalate-Based OpenFramework Constructed from Unsupported AgI…AgI Interactions [J]. Angew Chem Int Ed,2007,46:7579-7582.
[58] Pang H J,Peng J, Zhang C J, et al. A polyoxometalate-encapsulated3D porous metal–organicpseudo-rotaxane framework [J]. Chem Commun,2010,46:5097-5099.
[59]Gao Y Z，Xu Y Q，Han Z G et a1．Syntheses，structures and properties of3D inorganic—organichybrid frameworks constructed from lanthanide polymer and Keggin—type tungstosilicate． J．Solid StateChem．，2010，183(5)：1000—1006．
[60] S. Uchida, R. Kawamoto, T. Akatsuka, S. Hikichi, N. Mizuno,“Structures and Sorption Properties ofIonic Crystals of Macrocation-Dawson-Type Polyoxometalates with Different Charges”, Chem. Mater.2005,17,1367-1375.
[61] Zhao X Y, Liang D D, Liu S X, et al Two Dawson-Templated Three-Dimensional Metal-OrganicFrameworks Based on Oxalate-Bridged Binuclear Cobalt(II)/Nickel(II) SBUs and Bpy Linkers [J]. InorgChem,2008,47(16):7133-7138.
[62] Tian A X, Ying J, Peng J, et al. Assembly of a new Wells-Dawsonpolyoxometalate-templatedcompound based on Fe-btb complex [J]. Inorg Chem Commun,2008,11:1132-1135.
[63] Zhang C D, Liu S X, Ma F J, et al. Coordination between [H12P2W12O48]2-and antimony(III): synthesisand characterization of sandwich complex derived from the new {P2W13O51} fragment [J]. DaltonTrans,2010,39(34):8033-8037.
[64] Pradeep C P, Long D L, K gerler P, et al. Controlled assembly and solution observation of a2.6nmpolyoxometalate ‘super’ tetrahedron cluster:[KFe12(OH)18(α-1,2,3-P292W15O56)4][J]. Chem.Commun.,2007,(41):4254-4256.
[65]L．Ni，F．Hussain， G．R．Patzke，et al. Lanthanoid-Containing Open Wells_DawsonSilicotungstates:Synthesis, Crystal Structures, and Properties[J]. Inorg. Chem.2011,50,4944–4955．
[66] Li Y G, Dai L M, Wang Y H, et al. A new molybdenum-oxide-based organic-inorganic hybridframework templated by double-Keggin anions [J]. Chem Commun,2007,2593-2595.
[67] Ren Y P, Kong X J, Long L S, et al. Anion-Dependent Assembly of Cyclic Structure [J]. Cryst Growth&Des,2006,6(2):572-576.
[68] Zhai Q G, Wu X Y, Chen S M, et al. Keggin polyoxometalates-supported assembly of2Dsupramolecular isomers: Synthesis, crystal structures and characteristics of two novel hybridhost-guestcomplexes [J]. Inorg Chim Acta,2007,360:3484-3492.
[69] Lan Y Q, Li S L, Shao K Z, et al. Combination of POMs and deliberately designed macrocations:arational approach for synthesis of POM-pillared metal-organic framework [J]. Dalton Trans,2009,940-947.
[70]Dai L M，You W S，Li Y G et a1．A new p01yoxometalate-templated MoV-oxide-basedorganic-inorganic hybrid framework wi th honeycomb-l ike nanochannel s．Chem．Commun．，2009，2721-2723．
[71] Duan C Y, Wei M L, Guo D, et al. Crystal Structures and Properties of Large ProtonatedWaterClusters Encapsulated by Metal-Organic Frameworks [J]. J Am Chem Soc,2010,132(10):3321-3330.
[72] Jency Thomas, Dinesh Kumar, Arunachalam Ramanan et al. Crystallization of phosphomolybdateclusters mediated by copper azole complexes:Influence of pH and temperature [J]. Inorg Chim Acta2013,396,126–135.
[73] Du D Y, Qin J S, Li Y G, et al. An unprecedented3D8-connected pure inorganic framework based onnanosized {[Na12PO16H24]C[P4Mo6O31H6]4}15-clusters and zinc cationsw [J]. Chem. Commun,2011,47,2832–2834.
[74] Wang X L, Cao J J, Liu G C,et al. Ligands directed versatile cadmium-bis(triazole) metal–organicfragments to generate three new two dimensional complexes based on polymolybdenum phosphate [J].Inorg Chim Acta2013,402,6–11.
[75] Wang X L, Cao J J, Hou J L,et al. One inorganic–organic hybrid derived from reducedmolybdophosphate and trinuclear cadmium(II) fragment [J]. Chinese Chemical Letters2013,24,877–880.
[76] Mundit L A and Haushalter R C. Hydrothermal Synthesis of a Layered Zinc Molybdenum Phosphatewith Octahedral and Tetrahedral Zinc: Structure of (TMA)2(H3O)2[Zn3MO12O30(HP04)2(H2P04)6]·11.5H20[J]. Inorg. Chem.1992,31,3050-3053.
[77] Meyer L A and Haushalter R C, Hydrothermal synthesis, structure, and sorption sroperties of the newmicroporous ferric molybdenum phosphates [(CH3)4N]2(NH4)2[Fe2M012030(H2P04)6(HPO4)2].nH20and
[(CH3)4N]2Na4[Fe3M012030(HxP04)8]·nH20[J]. Inorg. Chem.1993,32,1579-1586.
[78] Yuan M, Wang E B, Lu Y, et al. A novel one-dimensional manganese phosphomolybdate withrectangular cavities:[H3N(CH2)4NH3](H3O)2{[Mn(phen)2]4[MnMov12O30(HPO4)6(H2PO4)2]}·4H2O[J]. Inorg. Chem. Commun.2002,5,505–508.
[79] Ma Y, Li Y G, Wang E B, et al. Syntheses, Structure Characterizations and Fluorescent Properties ofTwo Reduced Molybdenum (V) PhosphatesFunctionalized by Zinc Coordination Complexes[J]. J. Clust.Sci.2006,17,167-181.
[80] Zhang X, Xu J Q, Yu J H, et al. Structural characterizations and magnetic properties of three newreduced molybdenum phosphates[J]. J. Solid. StateChem.2007,180,1949–1956.
[81] Zhang L J, Zhou Y S, Li X Q, et al. Coordination Chemistry of the Magic Inorganic Building Block{FeII[Mo6P4O31]2}: Hydrothermal Synthesis and Crystal Structure of a New Reduced FerrousMolybdophosphate[J]. J. Clust.Sci.2007,18,921–933.
[82] Natalia M. Laptash, Irina G. Maslennikova, Arseny B. Slobodyuk, et al. Bonding and Structure ofOxofluoroniobate-Based Glasses [J]. Inorg. Chem.2013,52,57225728.
[83] Hongcheng Lu, Romain Gautier, Kenneth R. Poeppelmeier,et al. Nonlinear Active Materials: AnIllustration of Controllable Phase Matchability [J]. J. Am. Chem. Soc.2013,135,1194211950.
[84] Stomberg R．Acta.Chem.Scand，1984，38A(8)：603—607．
[85] Davidovich R.L.,Levchishina T.F．，Kaidalova T.A.，Sergienko V.I.,J.Less-Common.Metals,1972,27(1)：35—43．
[86] A.J.Norquist，C. L.Stern，K．R．Poeppelmeier, et al., Inorg.Chem.[J]，1999，38(15)：3448-3449.
[87] M.E,WeIk，A.J.Norquist，K．R．Poeppelmeier, et al., Inorg.Chem.[J]，2002，41(20)：5119-5125.
[88] K．I．Heather，E．K．Janet，K．R．Poeppelmeier, et al., Inorg.Chem.[J]，2005，44(4)：884-895．
[89]贺庆林．东北师范大学博士学位论文，1999．6
[90]朱刚，唐宗薰.西北大学硕士论文，2006.6
[1] Kuang X F, Wu X Y, Yu R M, et al. Assembly of a metal–organic framework by sextupleintercatenation of discrete adamantane-like cages [J]. Nature Chem,2010,2:461-465.
[2] Deng Q, HuangY L, Cai T J,et al. Crystal structure and catalytic properties of three inorganic–organic hybrid constructed from heteropolymolybdate and aminopyridine [J].Journal of SolidState Chemistry,2013,200,60–69.
[3] Hagrman D, Zubieta C, Rose D J, et al. Composite Solids Constructed From One-DimensionalCoordination Polymer Matrices and Molybdenum Oxide Subunits: Polyoxomolybdate Clusterswithin [{Cu(4,4’-bpy)}4Mo8O26] and [{Ni(H2O)2(4,4’-bpy)2}2Mo8O26] and One-DimensionalOxide Chains in [{Cu(4,4’-bpy)}4Mo15O47]·8H2O [J]. Angew. Chem., Int. Ed. Engl.,1997,36:873-875.
[4] Hu Y Y, Xiao L N, Wang Y,et al. New compounds based on polyoxometalates and transitionmetal complexes with a lower positive charge [J]. Polyhedron,2013,56,152–159.
[5] Zhang Y, Han X B, Wang E B, et al. A {Ni7} cluster-containing sandwich-typephosphotungstate functionalized by organic bisphosphonate ligands and its two-dimensionalsupramolecular structure [J]. Chinese Chemical Letters,2013,24,581–584.
[6] Zhang C H, Chen Y G, Liu S X,et al. Supramolecular compounds constructed by main groupmetals,polyoxotungstates and polyaminepolycarboxylate [J]. Solid State Sciences,2013,20,80–85.
[7] Yao S, Yan J H, Wang E B, et al. Integration of Ln-Sandwich POMs into Molecular PorousSystems Leading to Self-Assembly of Metal–POM Framework Materials [J]. Eur. J. Inorg. Chem.2013,4770–4774.
[8] Yu T T, Ma H Y, Li S B, et al. Interdigitated architectures assembled from α-metatungstatesand lanthanide–organic complexes [J]. Inorg Chem Comm,2013,33,43–47.
[9] Merinda R. Healey, Robert W. Gable, Chris Ritchie, et al. Accessing yttrium–polyoxometalate–carboxylate hybrids from a versatile arsenotungstate(III) precursor [J]. Polyhedron,2013,64,13–19.
[10] Zhao X F, Sun X W, Han Z G,et al.Two new polyoxometalate-based hybrids consisting ofKeggin-type clustermodified by{Ag4} group [J]. Journal of Solid State Chemistry,2013,207,178–183.
[11] Y.-K. Lu, X.-B. Cui, Y. Chen, J.-N. Xu, Q.-B. Zhang, Y.-B. Liu, J.-Q. Xu, T.-G. Wang (2009).J. Solid State Chem.182,2111.
[12] C. Rocchiccioli-Deltcheff, M. Fournier, R. Franck, R. Thouvenot (1983). Inorg. Chem.22,207.
[13] Bu.P.Teng and G.D.Stucy,Template symmetry effect in open-framework synthesis:a newvanadium(IV)phosphate,J. Chem.Soc.,Chem.Commun.,1995,1337.
[14]C.L. Meng, P.P. Zhang, J. Peng, X. Wang, Y. Shen, M.G. Liu, D.D. Wang, K. Alimaje (2012). J.Clust. Sci.23,567.
[15] X. Wang, J. Peng, M.G. Liu, D.D. Wang, C.L. Meng, Y. Li, Z.Y. Shi (2012). CrystEngComm.14,3220.
[16] Sadakane M, Steckhan E, Electrochemical Properties of Polyoxometalates as Electrocatalysts[J].Chem Rev,1998,98(1):219-238.
[17] M. T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin,1983.
[18]Gao S，Liu J W，Huo L H，et a1．Inorg Chem Commun，2005,8,361—364．
[1] A special issue for polyoxometalates edited by C．L Hill，Chem．Rev．98(1998)．
[2] Rinta Sato, Kosuke Suzuki, Noritaka Mizuno,et al. Heterodinuclear Lanthanoid-ContainingPolyoxometalates: Stepwise Synthesis and Single-Molecule Magnet Behavior [J]. Chem. Eur. J.2013,19,12982–12990.
[3] Chen H L, Yang Y, Wu L X,et al. Synthesis, Structural Characterization, andThermoresponsivity of Hybrid Supramolecular Dendrimers Bearing a Polyoxometalate Core [J].Chem. Eur. J.2013,19,11051–11061.
[4] Chai F, Chen Y P, Yang Z,et al. Synthesis and characterization of a new Hervé-typetungstoantimonite based on a-[SbW9O33]9-unit [J]. Journal of Molecular Structure,2013,1051,101–106.
[5] I.D. Holclajtner-Antunovic, A. Popa, D.V. Bajuk-Bogdanovic,et al. Synthesis andcharacterization of acid silver salts of12-tungstophosphoric acid [J]. Inorganica Chimica Acta,2013,407,197–203.
[6] Wang B, Xu L X, Meng R Q,et al. A new vanadium(IV)-bridged polyoxotungstate containingmixed valence-antimony(III,V)[J]. Inorganica Chimica Acta,2013,405,274–278.
[7] Beno t Riflade, Julie Oble, Ludwig Chenneberg,et al. Hybrid polyoxometalate palladacycles:DFT study and application to the Heck reaction [J].Tetrahedron,201369,5772–5779.
[8] Yao S, Wu H L, Wang E B,et al.‘‘S’’-shaped isopolyoxotungstate cluster decorated bycalcium ions [J]. Chinese Chemical Letters,2013,24,283–286.
[9] Liu D D, Chen Y G,et al. Coordination polymers of lanthanide elements and metatungstate:Syntheses, structure and magnetic property [J]. Inorganica Chimica Acta,2013,401,70–75.
[10] Duan H, Zhang Z M, Wang E B et al. Sandwich-type tungstoantimonates decorated by theheterometallic3d–5p clusters [J]. Inorg Chem Comm,2013,33,90–94.
[11] Li Y Z, Luo J, Niu J Y,et al. Synthesis, characterization, magnetic and electrochemicalproperties of a new3D hexa-copper-substituted germanotungstate [J]. Journal of Solid StateChemistry,2013,205,82–90.
[12] Jun Iijima, Haruo Naruke,et al. Synthesis and structural characterization of [CeIV(a2-P2W17O161)2]6-in the solid state and in aqueous solution [J]. Journal of Molecular Structure,2013,1040,33–38.
[13]Sadakane M, Steckhan E. Electrochemical Properties of Polyoxometalates as Electrocatalysts[J]. Chem. Rev.1998,98:219–237.
[14]Sha J Q, Peng J, Tian A X, Liu H S, Chen J, Zhang P P, Su Z M. Assembly of MultitrackCu-N Coordination Polymeric Chain-Modified Polyoxometalates Influenced by PolyoxoanionCluster and Ligand [J]. Cryst. Growth Des.2007,7:2535–2541.
[15] Dias H V R, Diyabalanage H V K, Rawashdeh-Omary M A, et al.[J]. BrightPhosphorescence of a Trinuclear Copper(I) Complex: Luminescence Thermochromism,Solvatochromism, and “Concentration Luminochromism” J. Am. Chem. Soc.,2003,125,12072-12073.
[1] M. T. Pope, Heteropoly and Isopoly Oxometalates, Springer, New York1983.
[2] Wei J J, Yang L, Niu J Y,et al. A Series of Multi-Dimensional Lanthanide-Containing Peroxoisopolymolybdates [J]. Cryst. Growth Des.2013,13,35543560.
[3] Guohui Sima, Li Q, Zhu Y,et al. Organoimido-Derivatized Hexamolybdates with a RemoteCarboxyl Group: Syntheses and Structural Characterizations [J]. Inorg. Chem.2013,52,65516558.
[4] Lin H Y, Xu C, Wang X L,et al. Two isostructural3D metal–organic frameworks constructedfrom1D [H2n2Mo4O14]nchains and the flexible bis-pyridyl-bis-amide ligand [J]. Inorg ChemComm,2013,36,81–85.
[5] Kari Darling, Tiffany M. Smith, Jose Vargas,et al. Polyoxometalate clusters as buildingblocks for oxide materials:Synthesis and structure of a three-dimensional copper-pyrazinetetrazolate/Keggin assembly [J]. Inorg Chem Comm,2013,32,1–4.
[6] Gu J, Jiang X, Su Z H,et al. Self-assembly of c-octamolybdate-based frameworks decoratedby1,3-bis(4-pyridyl)propane through covalent bond [J]. Inorganica ChimicaActa,2013,400,210–214.
[7] Soyeb Pathan, Anjali Patel,et al. Solvent free clean selective oxidation of alcohols catalyzedby mono transition metal (Co, Mn, Ni)-substituted Keggin-phosphomolybdates using hydrogenperoxide [J].Applied Catalysis A: General,2013,459,59–64.
[8] Yang Y Y, Xu L, Li F Y,et al. pH-dependent assembly of1D–2D structures based on both{V10O28} and [NiMo46O24H6]units: Synthesis, structure and magnetic properties [J]. Inorg ChemComm,2013,33,142–146.
[9] Guo J, Yang J, Ma J F,et al. Two new polyoxometalate-templated supramolecular compoundsconstructed by a new tridentate ligand2,4,6-tris[1-(4-oxidroxypyridinium)-ylmethyl]-mesitylene[J]. Inorganica ChimicaActa,2013,400,51–58.
[10] Shi S Y, Teng H H, Chang L M,et al. New compounds constructed from bi-antimony cappedKeggin polyoxoanions and different coordination fragments [J]. Inorganica ChimicaActa,2013,399,172–176.
[11]BROWNI ALTERMATTD.Bond-valence parameters obtained from asystematic analysis ofthe inorganic crystal structure databade［J］.ActaCryst，1985，41B：244-247.
[12] Sadakane M, Steckhan E, Electrochemical Properties of Polyoxometalates asElectrocatalysts[J]. Chem Rev,1998,98:219-237.
[1] Li L, Zhang S Q, Xu L J,et al. An Intensely Luminescent Metal Organic Framework Based ona Highly Light-Harvesting Dyclo-Metalated Iridium(III) Unit Showing Effective Detection ofExplosives [J]. Inorg. Chem.2013,52,1232312325.
[2] Yan Y, Du P, Ma J F,et al. A Series of Coordination Polymers Constructed by Flexible4Substituted Bis(1,2,4-triazole) Ligands and Polycarboxylate Anions:Syntheses, Structures, andPhotoluminescent Properties [J]. Cryst. Growth Des.2013,13,47814795.
[3] Michele R. Chierotti, Andrea Rossin, Roberto Gobetto,et al. Interaction between a Transition-Metal Fluoride and a Transition-Metal Hydride: Water-Mediated Hydrofluoric Acid EvolutionFollowing Fluoride Solvation [J]. Inorg. Chem.2013,52,1261612623.
[4] Petri Seppala,Enrique Colacio, Antonio J. Mota,et al. Structural Diversity due to AminoAlcohol Ligands Leading to Rare μ4Hydroxo-Bridged Tetranuclear and “Bicapped Cubane”Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study [J].Inorg. Chem.2013,52,1109611109.
[5] Pau Díaz-Gallifa,Oscar Fabelo, Jorge Pasan,et al. Synthesis, Crystal Structure and MagneticCharacterization of a Series of CuII LnIIIHeterometallic(Ln=La, Ce, Pr, Nd and Sm) MetalOrganic Compounds with an Unusual Single Crystal to Single Crystal Phase Transition [J].Cryst.Growth Des.,2013,13,47354745.
[6] Huang K B, Chen Z F, Liu Y C,et al. Copper(II/I) complexes of5-pyridin-2-yl-[1,3]dioxolo
[4,5-g] isoquinoline: Synthesis, crystal structure, antitumor activity and DNA interaction [J].European Journal of Medicinal Chemistry,2013,70,640648.
[7] Chandan Adhikary, Sourajit Banerjee, Sandra Ianelli,et al. Copper(II) azide complexes withNNO donor ligands: Syntheses, structure, catalysis and biological studies [J].Polyhedron,2013,65,48–53.
[8] Elena K. Beloglazkina, Alexander G. Majouga, Andrei V. Mironov,et al. Synthesis, X-raycrystallography and electrochemistry of three novel copper complexes with imidazole-containinghydantoin and thiohydantoins [J]. Polyhedron,2013,63,15–20.
[9] Lu H H, Romain Gautier, Kenneth R. Poeppelmeier,et al. Nonlinear Active Materials: AnIllustration of Controllable Phase Matchability [J]. J. Am. Chem. Soc.2013,135,1194211950.
[10] Romain Gautier and Kenneth R. Poeppelmeier,et al. Alignment of Acentric Units in InfiniteChains: A “Lock and Key” Model [J].Cryst. Growth Des.2013,13,40844091.
[11] P.Halasymani, C. L.Stern,M.J.Willis, et al., Inorg.Chem.[J],1996,35:1367-1371.
[12N.G.Furmanova,M.Kh.Rabadanov,M.S.Fonar, et al., Kristallografiya[J],2008,53:273.
[13] JIN Su-Rong(靳素荣),ZHANG Lian-Meng(张联盟),ZHAO Wei-Feng(赵卫峰), eta1..Journal of Wuhan University of Technology (武汉理工大学学报)[J],2005,27(4):2-3
[14] Norquist A. J., Welk M. E., Stern C. L., et al., Chem. Mater.[J],2000,12:1905-1909
[15]Gao S.,Liu J. W.,Huo L.H.,et a1.,Inorg.Chem.Commun.[J],2005,8:361-364
[2]王恩波，李阳光，鹿颖等，多酸化学概论[M]，长春：东北师范大学出版社，2007,4.
[3] Hu J K, Yu X Y, Luo Y H, et al. Hydrothermal syntheses and crystal structures of two novel Inorganic–organic hybrid compounds based on saturated α-Keggin phosphomolybdate clusters [J]. Inorg ChemComm,2013,32,37–41.
[4] Yuji Kikukawa, Kosuke Suzuki, Noritaka Mizuno, et al. Synthesis, Structure Characterization, andReversible Transformation of a Cobalt Salt of a Dilacunary γ Keggin Silicotungstate and Sandwich-TypeDi-and Tetracobalt-Containing Silicotungstate Dimers [J]. Inorg Chem.2013,52,86448652.
[6] Duan H, Zhang Z M, Wang E B, et al. Sandwich-type tungstoantimonates decorated by theheterometallic3d–5p clusters[J]. Inorg Chem Comm,2013,33,90–94.
[7] Yin P C, Li T, Long D L, et al. Exploring the Programmable Assembly of a Polyoxometalate OrganicHybrid via Metal Ion Coordination[J]. J Am Chem Soc,2013,135,1342513432.
[8] Kazuhiro Uehara, Takamichi Oishi, Noritaka Mizuno, et al. Synthesis and Characterization ofMolecular Hexagons and Rhomboids and Subsequent Encapsulation of Keggin-Type Polyoxometalates byMolecular Hexagons [J]. Inorg Chem.2013,52,1120011209.
[9] Shi Z Y, Peng J, Li Y G, et al. Assembly of multinuclear Ag complexes and Keggin polyoxometalatesadjusted by organic ligands:syntheses, structures and luminescence [J]. CrystEngComm,2013,15,7583–7588.
[10] Wu N, Qin Y, Wang E B, et al. Two layered copper–bis(triazole) assemblieswith Kegginpolyoxoanions as pendants: Syntheses, structures and photocatalytic properties [J]. Inorg Chem Comm,2013,37,174–177.
[11] Pedro I. Molina, Haralampos N. Miras, Leroy Cronin, et al. Exploring the Assembly ofSupramolecular Polyoxometalate Triangular Morphologies with Johnson Solid Cores:[(MnII(H2O)3)2(K{α-GeWII1910Mn2O38}3)][J]. Inorg. Chem.2013,52,92849289.
[12] Cui K Y, Li F Y, Xu L, et al. A3D all-inorganic architecture based on the [H2W112O42]0-building blockwith different alkalineearth metal linkers: crystal structures, surface photovoltage and photoluminescentproperties [J]. CrystEngComm,2013,15,4721–4729.
[13] Wang X, Zhang M M, Hao X L et al. Polyoxometalate-Induced New Self-Assemblies Based onCopper Ions and Bichelate-Bridging Ligands [J]. Cryst. Growth Des.2013,13,34543462.
[14] Raju Mekala, Sabbani Supriya, and Samar K. Das. Fate of a Giant {Mo72Fe30} Type PolyoxometalateCluster in an Aqueous Solution at Higher Temperature: Understanding Related Keplerate Chemistry, fromMolecule to Material[J]. Inorg. Chem.2013,52,97089710.
[15] Maxim N. Sokolov, Sergey A. Adonin, Dmitry A. Mainichev, et al. New {RuNO} Polyoxometalate
[PWI11O39RuI(NO)]4: Synthesis and Reactivity [J]. Inorg. Chem.2013,52,96759682.
[16] Yang L, Ma P T, Wang J P, et al. A Crown-Shaped24-Molybdate Cluster Constructed byOrganotriphosphonate Ligand [J]. Inorg. Chem.2013,52,82858287.
[17] Shi Z Y, Peng J, Yu X, et al. A new3D Keggin-POM based metal–organic framework of Cu andH2biim: Assembly and properties of fluorescence and electrochemistry [J]. Inorg Chem Comm,2013,28,85–89.
[18] Sayaka Uchida, Eri Takahashi, and Noritaka Mizuno. Porous Ionic Crystals Modified byPost-Synthesis of K2[Cr3O(OOCH)6(etpy)3]2[α-SiW12O40]·8H2O through Single-Crystal-to-Single-CrystalTransformation [J]. Inorg. Chem.2013,52,93209326.
[19] Cao G J,Rong C.(C6H6)4[H4GeMo12O40].1.5H2O: A New Polyoxomolybdate Obtained from In SituReaction [J]. J Clust Sci,2013,24,843–850.
[20] Wang X, Peng J, K Alimaje, et al. Two Keggin polyoxoanion-based hybrids composed of CuI/tbzsegments:Syntheses, structures and electrochemical properties [J]. Inorg Chem Comm,2013,36,141–145.
[21] Zhao J W, Shi D Y, Chen L J, et al. Tetrahedral Polyoxometalate Nanoclusters with TetramericRare-Earth Cores and Germanotungstate Vertexes [J]. Cryst. Growth Des.2013,13,43684377.
[22] Shi Z Y, Peng J, Zhang Z Y, et al.et al. Syntheses, structures and photoluminescence of twoDawson-based hybrid materials with polynuclear silver clusters [J]. Inorg Chem Comm,2013,33,105–108.
[23] Liu Z J,Yao S, Wang E B,et al. A polyoxometalate-based ionic crystal assembly from a heterometalliccluster and polyoxoanions with visiblelight catalytic activity [J].RSC Adv.,2013,3,20829.
[24] Amaia Iturrospe, Benat Artetxe, Santiago Reinoso,et al. Copper(II) Complexes of Tetradentate PyridylLigands Supported on Keggin Polyoxometalates: Single-Crystal to Single-Crystal TransformationsPromoted by Reversible Dehydration Processes [J]. Inorg. Chem.2013,52,30843093.
[25] Guo D, Teng S Y, Liu Z G,et al. Synthesis and Structure of [Co14-2Bi2(a or b-B-CoW9O34)2]Isomersand Their Catalytic Water Oxidation [J]. J Clust Sci,2013,24,549–558.
[26] Masooma Ibrahim, Xiang Y X, Ulrich Kortz,et al. Synthesis, Magnetism, and Electrochemistry of theNi14-and Ni5Containing Heteropolytungstates[Ni14(OH)6(H2O)10(HPO4)4(P2W15O56)4]34and
[Ni5(OH)4(H2O)4(β-GeW9O34)(β-GeW8O30(OH))]13[J]. Inorg. Chem.2013,52,83998408.
[27] Wang Y C, Li F Y, Xu L, et al. Multidimensional crystal frameworks based onHeteropoly bluebuilding block of [SiW610MoV2O40]:synthesis, structures and magnetic properties [J].Dalton Trans.,2013,42,5839.
[28] Li J S, Sang X J, Chen W L,et al. The research of a new polyoxometalates based photosensitizer ondye sensitized solar cell [J]. Inorg Chem Comm,2013,38,78–82.
[29] Zhang J, Chen W L, WangE B,et al. Synthesis and catalytic properties of novel POM@TiO2composite materials [J]. Inorg Chem Comm,2013,38,96–99.
[30] Zhang C H, Chen Y G, Liu S X,et al. Weakley sandwich-type anion in organic–inorganic hybridcompound with3D framework [J]. Inorg Chem Comm,2013,29,45–48.
[31] Cassan-Pastor N，Baker L C W. Magnetic properties of mixed-valence heteropoly blues interactionswith complexes containjing paramagnetic atoms in obvious sites as well as ‘blue’electrodes delocalizedover polytungstate frameworks[J]．J Am Chem Soc，1992，114(26)，10384—10389．
[32] Zheng X P, Lu Y, Wang E B,et al. Two new metal–organic frameworks based on cyclicdodecanuclear copper units[J]. Inorg Chem Comm,2013,33,29–32.
[33] Li X M, Chen Y G, Su C N,et al. Functionalized Pentamolybdodiphosphate-Based Inorganic-OrganicHybrids: Synthesis, Structure, and Properties [J].Inorg. Chem.2013,52,1142211427.
[34] Shen J Q, Yao S, Zhang Z M,et al. Self-assembly and photocatalytic property ofgermanoniobate [H6Ge4Nb16O56]10: encapsulating four {GeO4} tetrahedra within a {Nb16} cage[J].DaltonTrans.,2013,42,5812.
[35] Liu D, Lu, Wang E B,et al. Polyoxometalate-based purely inorganic porous frameworks with selectiveadsorption and oxidative catalysis functionalities [J].Chem. Commun.,2013,49,3673.
[36] Wu H H, Yao S, Zhang Z M,et al. Heterometallic appended {MMnIII4} cubanes encapsulated bylacunary polytungstate ligands [J]. Dalton Trans.,2013,42,342.
[37] Han Q X, He C, Niu J Y,et al. Engineering Chiral Polyoxometalate Hybrid Metal OrganicFrameworks for Asymmetric Dihydroxylation of Olefins [J]. J. Am. Chem. Soc.2013,135,1018610189
[38] Toshihiro Y．Photo and Electrochromism of PolyoxometalaIes and Pelaled Material[J]．Chem Rev，1998．98：307-325.
[39]王恩波，胡长文，许林等，多酸化学导论[M]，北京：化学工业出版社，1997，14-47.
[40] M. I. Khan, S. Cevik, R. Hayashi,“First12-tungstovanadate Keggin compound:synthesis and crystalstructure of [Me4N]7[VW12O40]·15H2O.” J.Chem. Soc., Dalton Trans1999,1651-1654.
[41] A. Yokoyama, T. Kojima, K. Ohkubo, S. Fukuzumi,“A discrete conglomerate of a distortedMo(V)-porphyrin with a directly coordinated keggin-type polyoxometalate”, Chem. Commun.,2007,3997-3999.
[42] Y. Xu, J.Q. Xu, K.L. Zhang, Y. Zhang, X.Z. You,“Keggin unit supported transition metal complexes:hydrothermal synthesis and characterization of[Ni(2,2’-bipy)3]1.5[PW12O40Ni(2,2’-bipy)2(H2O)]·0.5H2Oand [Co(1,10’-phen)3]1.5[PMo12O40Co(1,10’-phen)2(H2O)]·0.5H2O”, Chem. Commun.2000,153-154.
[43] J.P. Wang, Q. Ren, J.W. Zhao, J.Y. Niu,“A novel Keggin-type tungstogermanate dimer bearingdinuclear copper-organic coordination ions:{H8[Cu(phen)(μ2-CH3COO)2Cu(phen)(H2O)]2[Ge2W23CuO80]}·24H2O”,Inorganic Chemistry Communications2006,9,1281-1285.
[44] Inman C, Knaust J M, Keller S W. A polyoxometallate-templated coordination polymer: synthesis andcrystal structure of [Cu3(4,4’-bipy)5(MeCN)2]PW12O40·2C6H5CN [J]. J Chem Soc, Chem Commun,2002,156-157.
[45] Knaust J M, Inman C, Keller S W. A host-guest complex between a metal-organic cyclotriveratryleneanalog and a polyoxometalate:[Cu6(4,7-phenanthroline)8(MeCN)4]2PM12O40(M=Mo or W)[J]. ChemCommun,2004,492-493.
[46] Kong X J, Ren Y P, Zheng P Q, et al. Construction of Polyoxometalates-Based CoordinationPolymersthrough Direct Incorporation between Polyoxometalates and the Voids in a2D Network [J]. InorgChem,2006,45(26):10702-10711.
[47] Meng F X, Chen Y G, Liu H B, Assembly of two novel coordination polymers constructedfrommetal-organic framework and Keggin-template [J]. J Mole Struct,2007,837:224-230
[48] E. Burkholder, V. Golub, C.J. O’Connor, J. Zubieta,“Hydrothermal synthesis f a one-dimensionalbimetallic mixed valence oxide [{Cu4(terpy)4(PO4)(H2O)2}{WVI10WV2O36(PO4)}]·5H2O, a materialconstructed from{PW5-12O40}and novel [{Cu4(terpy)4(PO5+4)(H2O)2}cluster building blocks”,Inorg. Chem.Commun.,2004,7,363-366.
[49] S. Chang, C. Qin, E.B. Wang, Y.G. Li, X.L. Wang,“New potassiumion-bridged chainlike assemblyfrom bisupporting Keggin units: K[M(phen)2(H2O)]2[PW12O40]·2H2O (M=Fe, Cu)”, Inorganic ChemistryCommunications2006,9,727-731.
[50] H. Jin, C. Qin, Y.G. Li, E.B. Wang,“[Cu5Cl(4,4’-bipy)5][SiW12O40]1.5H2O:A novel three-dimensionalframework constructed from polyoxometalate clusters and trinuclear Cu(I) complex”, Inorganic ChemistryCommunications2006,9,482-485.
[51] J.Q. Sha, J. Peng, H.S. Liu, B. Xue, J. Chen, A.X Tian, B.X. Dong, P.P. Zhang,“Controlled assemblyof two novel3D hexad-supporting Keggin-polyoxometalate derivatives:{[Cu(4,4’-bipy)]3[HnXW12O40]}
[4,4’-bipy]·2H2O (X=P, n=0; X=Si, n=1)”, Journal of MolecularStructure2007,871,85-91.
[52] J.X. Chen, T.Y. Lan, Y.B. Huang, C.X.Wei, Z.S. Li, Z.C. Zhang,“Hydrothermal synthesis, crystalstructure and properties of a3D-framework polyoxometalate assembly:[Ag(4,4’-bipy)](OH){[Ag(4,4’-bipy)]2[PAgW12O40]}·3.5H2O”, Journal of Solid State Chemistry2006,179,1904-1910
[53] S. Reinoso, P. Vitoria, J. M. Gutiérrez-Zorrilla, L. Lezama, LS. Felices, J.I.Beitia,“Inorganic-Metalorganic Hybrids Based on Copper(II)-Monosubstituted Keggin Polyanions and DinuclearCopper(II)-Oxalate Complexes. Synthesis, X-ray Structural Characterization, and Magnetic Properties”Inorg. Chem.,2005,44,9731-9742.
[54] Fan L L, Xiao D R, Wang E B, et al. An Unprecedented Fivefold Interpenetrating Network Based onPolyoxometalate Building Blocks [J]. Cryst Growth&Des,2007,7(4):592-594.
[55] Bassil B S, Dickman M H, Kammer B, et al. The Monolanthanide-ContainingSilicotungstates[Ln(β12-SiW11O39)2]3-(Ln=La, Ce, Sm, Eu, Gd, Tb, Yb, Lu): A Synthetic and StructuralInvestigation [J].Inorg. Chem.2007,46(7):2452-2458
[56] Jiang C J, Lesbani A, Kawamoto R, et al. Channel-Selective Independent Sorption and Collection ofHydrophilic and Hydrophobic Molecules by Cs2[Cr3O(OOCC2H5)6(H2O)3]2[α-SiW12O40] Ionic Crystal [J].JAm Chem Soc,2006,128(44):14240-14241
[57] Streb C, Ritchie C, Long D L, et al. Modular Assembly of a Functional Polyoxometalate-Based OpenFramework Constructed from Unsupported AgI…AgI Interactions [J]. Angew Chem Int Ed,2007,46:7579-7582.
[58] Pang H J,Peng J, Zhang C J, et al. A polyoxometalate-encapsulated3D porous metal–organicpseudo-rotaxane framework [J]. Chem Commun,2010,46:5097-5099.
[59]Gao Y Z，Xu Y Q，Han Z G et a1．Syntheses，structures and properties of3D inorganic—organichybrid frameworks constructed from lanthanide polymer and Keggin—type tungstosilicate． J．Solid StateChem．，2010，183(5)：1000—1006．
[60] S. Uchida, R. Kawamoto, T. Akatsuka, S. Hikichi, N. Mizuno,“Structures and Sorption Properties ofIonic Crystals of Macrocation-Dawson-Type Polyoxometalates with Different Charges”, Chem. Mater.2005,17,1367-1375.
[61] Zhao X Y, Liang D D, Liu S X, et al Two Dawson-Templated Three-Dimensional Metal-OrganicFrameworks Based on Oxalate-Bridged Binuclear Cobalt(II)/Nickel(II) SBUs and Bpy Linkers [J]. InorgChem,2008,47(16):7133-7138.
[62] Tian A X, Ying J, Peng J, et al. Assembly of a new Wells-Dawsonpolyoxometalate-templatedcompound based on Fe-btb complex [J]. Inorg Chem Commun,2008,11:1132-1135.
[63] Zhang C D, Liu S X, Ma F J, et al. Coordination between [H12P2W12O48]2-and antimony(III): synthesisand characterization of sandwich complex derived from the new {P2W13O51} fragment [J]. DaltonTrans,2010,39(34):8033-8037.
[64] Pradeep C P, Long D L, K gerler P, et al. Controlled assembly and solution observation of a2.6nmpolyoxometalate ‘super’ tetrahedron cluster:[KFe12(OH)18(α-1,2,3-P292W15O56)4][J]. Chem.Commun.,2007,(41):4254-4256.
[65]L．Ni，F．Hussain， G．R．Patzke，et al. Lanthanoid-Containing Open Wells_DawsonSilicotungstates:Synthesis, Crystal Structures, and Properties[J]. Inorg. Chem.2011,50,4944–4955．
[66] Li Y G, Dai L M, Wang Y H, et al. A new molybdenum-oxide-based organic-inorganic hybridframework templated by double-Keggin anions [J]. Chem Commun,2007,2593-2595.
[67] Ren Y P, Kong X J, Long L S, et al. Anion-Dependent Assembly of Cyclic Structure [J]. Cryst Growth&Des,2006,6(2):572-576.
[68] Zhai Q G, Wu X Y, Chen S M, et al. Keggin polyoxometalates-supported assembly of2Dsupramolecular isomers: Synthesis, crystal structures and characteristics of two novel hybridhost-guestcomplexes [J]. Inorg Chim Acta,2007,360:3484-3492.
[69] Lan Y Q, Li S L, Shao K Z, et al. Combination of POMs and deliberately designed macrocations:arational approach for synthesis of POM-pillared metal-organic framework [J]. Dalton Trans,2009,940-947.
[70]Dai L M，You W S，Li Y G et a1．A new p01yoxometalate-templated MoV-oxide-basedorganic-inorganic hybrid framework wi th honeycomb-l ike nanochannel s．Chem．Commun．，2009，2721-2723．
[71] Duan C Y, Wei M L, Guo D, et al. Crystal Structures and Properties of Large ProtonatedWaterClusters Encapsulated by Metal-Organic Frameworks [J]. J Am Chem Soc,2010,132(10):3321-3330.
[72] Jency Thomas, Dinesh Kumar, Arunachalam Ramanan et al. Crystallization of phosphomolybdateclusters mediated by copper azole complexes:Influence of pH and temperature [J]. Inorg Chim Acta2013,396,126–135.
[73] Du D Y, Qin J S, Li Y G, et al. An unprecedented3D8-connected pure inorganic framework based onnanosized {[Na12PO16H24]C[P4Mo6O31H6]4}15-clusters and zinc cationsw [J]. Chem. Commun,2011,47,2832–2834.
[74] Wang X L, Cao J J, Liu G C,et al. Ligands directed versatile cadmium-bis(triazole) metal–organicfragments to generate three new two dimensional complexes based on polymolybdenum phosphate [J].Inorg Chim Acta2013,402,6–11.
[75] Wang X L, Cao J J, Hou J L,et al. One inorganic–organic hybrid derived from reducedmolybdophosphate and trinuclear cadmium(II) fragment [J]. Chinese Chemical Letters2013,24,877–880.
[76] Mundit L A and Haushalter R C. Hydrothermal Synthesis of a Layered Zinc Molybdenum Phosphatewith Octahedral and Tetrahedral Zinc: Structure of (TMA)2(H3O)2[Zn3MO12O30(HP04)2(H2P04)6]·11.5H20[J]. Inorg. Chem.1992,31,3050-3053.
[77] Meyer L A and Haushalter R C, Hydrothermal synthesis, structure, and sorption sroperties of the newmicroporous ferric molybdenum phosphates [(CH3)4N]2(NH4)2[Fe2M012030(H2P04)6(HPO4)2].nH20and
[(CH3)4N]2Na4[Fe3M012030(HxP04)8]·nH20[J]. Inorg. Chem.1993,32,1579-1586.
[78] Yuan M, Wang E B, Lu Y, et al. A novel one-dimensional manganese phosphomolybdate withrectangular cavities:[H3N(CH2)4NH3](H3O)2{[Mn(phen)2]4[MnMov12O30(HPO4)6(H2PO4)2]}·4H2O[J]. Inorg. Chem. Commun.2002,5,505–508.
[79] Ma Y, Li Y G, Wang E B, et al. Syntheses, Structure Characterizations and Fluorescent Properties ofTwo Reduced Molybdenum (V) PhosphatesFunctionalized by Zinc Coordination Complexes[J]. J. Clust.Sci.2006,17,167-181.
[80] Zhang X, Xu J Q, Yu J H, et al. Structural characterizations and magnetic properties of three newreduced molybdenum phosphates[J]. J. Solid. StateChem.2007,180,1949–1956.
[81] Zhang L J, Zhou Y S, Li X Q, et al. Coordination Chemistry of the Magic Inorganic Building Block{FeII[Mo6P4O31]2}: Hydrothermal Synthesis and Crystal Structure of a New Reduced FerrousMolybdophosphate[J]. J. Clust.Sci.2007,18,921–933.
[82] Natalia M. Laptash, Irina G. Maslennikova, Arseny B. Slobodyuk, et al. Bonding and Structure ofOxofluoroniobate-Based Glasses [J]. Inorg. Chem.2013,52,57225728.
[83] Hongcheng Lu, Romain Gautier, Kenneth R. Poeppelmeier,et al. Nonlinear Active Materials: AnIllustration of Controllable Phase Matchability [J]. J. Am. Chem. Soc.2013,135,1194211950.
[84] Stomberg R．Acta.Chem.Scand，1984，38A(8)：603—607．
[85] Davidovich R.L.,Levchishina T.F．，Kaidalova T.A.，Sergienko V.I.,J.Less-Common.Metals,1972,27(1)：35—43．
[86] A.J.Norquist，C. L.Stern，K．R．Poeppelmeier, et al., Inorg.Chem.[J]，1999，38(15)：3448-3449.
[87] M.E,WeIk，A.J.Norquist，K．R．Poeppelmeier, et al., Inorg.Chem.[J]，2002，41(20)：5119-5125.
[88] K．I．Heather，E．K．Janet，K．R．Poeppelmeier, et al., Inorg.Chem.[J]，2005，44(4)：884-895．
[89]贺庆林．东北师范大学博士学位论文，1999．6
[90]朱刚，唐宗薰.西北大学硕士论文，2006.6
[1] Kuang X F, Wu X Y, Yu R M, et al. Assembly of a metal–organic framework by sextupleintercatenation of discrete adamantane-like cages [J]. Nature Chem,2010,2:461-465.
[2] Deng Q, HuangY L, Cai T J,et al. Crystal structure and catalytic properties of three inorganic–organic hybrid constructed from heteropolymolybdate and aminopyridine [J].Journal of SolidState Chemistry,2013,200,60–69.
[3] Hagrman D, Zubieta C, Rose D J, et al. Composite Solids Constructed From One-DimensionalCoordination Polymer Matrices and Molybdenum Oxide Subunits: Polyoxomolybdate Clusterswithin [{Cu(4,4’-bpy)}4Mo8O26] and [{Ni(H2O)2(4,4’-bpy)2}2Mo8O26] and One-DimensionalOxide Chains in [{Cu(4,4’-bpy)}4Mo15O47]·8H2O [J]. Angew. Chem., Int. Ed. Engl.,1997,36:873-875.
[4] Hu Y Y, Xiao L N, Wang Y,et al. New compounds based on polyoxometalates and transitionmetal complexes with a lower positive charge [J]. Polyhedron,2013,56,152–159.
[5] Zhang Y, Han X B, Wang E B, et al. A {Ni7} cluster-containing sandwich-typephosphotungstate functionalized by organic bisphosphonate ligands and its two-dimensionalsupramolecular structure [J]. Chinese Chemical Letters,2013,24,581–584.
[6] Zhang C H, Chen Y G, Liu S X,et al. Supramolecular compounds constructed by main groupmetals,polyoxotungstates and polyaminepolycarboxylate [J]. Solid State Sciences,2013,20,80–85.
[7] Yao S, Yan J H, Wang E B, et al. Integration of Ln-Sandwich POMs into Molecular PorousSystems Leading to Self-Assembly of Metal–POM Framework Materials [J]. Eur. J. Inorg. Chem.2013,4770–4774.
[8] Yu T T, Ma H Y, Li S B, et al. Interdigitated architectures assembled from α-metatungstatesand lanthanide–organic complexes [J]. Inorg Chem Comm,2013,33,43–47.
[9] Merinda R. Healey, Robert W. Gable, Chris Ritchie, et al. Accessing yttrium–polyoxometalate–carboxylate hybrids from a versatile arsenotungstate(III) precursor [J]. Polyhedron,2013,64,13–19.
[10] Zhao X F, Sun X W, Han Z G,et al.Two new polyoxometalate-based hybrids consisting ofKeggin-type clustermodified by{Ag4} group [J]. Journal of Solid State Chemistry,2013,207,178–183.
[11] Y.-K. Lu, X.-B. Cui, Y. Chen, J.-N. Xu, Q.-B. Zhang, Y.-B. Liu, J.-Q. Xu, T.-G. Wang (2009).J. Solid State Chem.182,2111.
[12] C. Rocchiccioli-Deltcheff, M. Fournier, R. Franck, R. Thouvenot (1983). Inorg. Chem.22,207.
[13] Bu.P.Teng and G.D.Stucy,Template symmetry effect in open-framework synthesis:a newvanadium(IV)phosphate,J. Chem.Soc.,Chem.Commun.,1995,1337.
[14]C.L. Meng, P.P. Zhang, J. Peng, X. Wang, Y. Shen, M.G. Liu, D.D. Wang, K. Alimaje (2012). J.Clust. Sci.23,567.
[15] X. Wang, J. Peng, M.G. Liu, D.D. Wang, C.L. Meng, Y. Li, Z.Y. Shi (2012). CrystEngComm.14,3220.
[16] Sadakane M, Steckhan E, Electrochemical Properties of Polyoxometalates as Electrocatalysts[J].Chem Rev,1998,98(1):219-238.
[17] M. T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin,1983.
[18]Gao S，Liu J W，Huo L H，et a1．Inorg Chem Commun，2005,8,361—364．
[1] A special issue for polyoxometalates edited by C．L Hill，Chem．Rev．98(1998)．
[2] Rinta Sato, Kosuke Suzuki, Noritaka Mizuno,et al. Heterodinuclear Lanthanoid-ContainingPolyoxometalates: Stepwise Synthesis and Single-Molecule Magnet Behavior [J]. Chem. Eur. J.2013,19,12982–12990.
[3] Chen H L, Yang Y, Wu L X,et al. Synthesis, Structural Characterization, andThermoresponsivity of Hybrid Supramolecular Dendrimers Bearing a Polyoxometalate Core [J].Chem. Eur. J.2013,19,11051–11061.
[4] Chai F, Chen Y P, Yang Z,et al. Synthesis and characterization of a new Hervé-typetungstoantimonite based on a-[SbW9O33]9-unit [J]. Journal of Molecular Structure,2013,1051,101–106.
[5] I.D. Holclajtner-Antunovic, A. Popa, D.V. Bajuk-Bogdanovic,et al. Synthesis andcharacterization of acid silver salts of12-tungstophosphoric acid [J]. Inorganica Chimica Acta,2013,407,197–203.
[6] Wang B, Xu L X, Meng R Q,et al. A new vanadium(IV)-bridged polyoxotungstate containingmixed valence-antimony(III,V)[J]. Inorganica Chimica Acta,2013,405,274–278.
[7] Beno t Riflade, Julie Oble, Ludwig Chenneberg,et al. Hybrid polyoxometalate palladacycles:DFT study and application to the Heck reaction [J].Tetrahedron,201369,5772–5779.
[8] Yao S, Wu H L, Wang E B,et al.‘‘S’’-shaped isopolyoxotungstate cluster decorated bycalcium ions [J]. Chinese Chemical Letters,2013,24,283–286.
[9] Liu D D, Chen Y G,et al. Coordination polymers of lanthanide elements and metatungstate:Syntheses, structure and magnetic property [J]. Inorganica Chimica Acta,2013,401,70–75.
[10] Duan H, Zhang Z M, Wang E B et al. Sandwich-type tungstoantimonates decorated by theheterometallic3d–5p clusters [J]. Inorg Chem Comm,2013,33,90–94.
[11] Li Y Z, Luo J, Niu J Y,et al. Synthesis, characterization, magnetic and electrochemicalproperties of a new3D hexa-copper-substituted germanotungstate [J]. Journal of Solid StateChemistry,2013,205,82–90.
[12] Jun Iijima, Haruo Naruke,et al. Synthesis and structural characterization of [CeIV(a2-P2W17O161)2]6-in the solid state and in aqueous solution [J]. Journal of Molecular Structure,2013,1040,33–38.
[13]Sadakane M, Steckhan E. Electrochemical Properties of Polyoxometalates as Electrocatalysts[J]. Chem. Rev.1998,98:219–237.
[14]Sha J Q, Peng J, Tian A X, Liu H S, Chen J, Zhang P P, Su Z M. Assembly of MultitrackCu-N Coordination Polymeric Chain-Modified Polyoxometalates Influenced by PolyoxoanionCluster and Ligand [J]. Cryst. Growth Des.2007,7:2535–2541.
[15] Dias H V R, Diyabalanage H V K, Rawashdeh-Omary M A, et al.[J]. BrightPhosphorescence of a Trinuclear Copper(I) Complex: Luminescence Thermochromism,Solvatochromism, and “Concentration Luminochromism” J. Am. Chem. Soc.,2003,125,12072-12073.
[1] M. T. Pope, Heteropoly and Isopoly Oxometalates, Springer, New York1983.
[2] Wei J J, Yang L, Niu J Y,et al. A Series of Multi-Dimensional Lanthanide-Containing Peroxoisopolymolybdates [J]. Cryst. Growth Des.2013,13,35543560.
[3] Guohui Sima, Li Q, Zhu Y,et al. Organoimido-Derivatized Hexamolybdates with a RemoteCarboxyl Group: Syntheses and Structural Characterizations [J]. Inorg. Chem.2013,52,65516558.
[4] Lin H Y, Xu C, Wang X L,et al. Two isostructural3D metal–organic frameworks constructedfrom1D [H2n2Mo4O14]nchains and the flexible bis-pyridyl-bis-amide ligand [J]. Inorg ChemComm,2013,36,81–85.
[5] Kari Darling, Tiffany M. Smith, Jose Vargas,et al. Polyoxometalate clusters as buildingblocks for oxide materials:Synthesis and structure of a three-dimensional copper-pyrazinetetrazolate/Keggin assembly [J]. Inorg Chem Comm,2013,32,1–4.
[6] Gu J, Jiang X, Su Z H,et al. Self-assembly of c-octamolybdate-based frameworks decoratedby1,3-bis(4-pyridyl)propane through covalent bond [J]. Inorganica ChimicaActa,2013,400,210–214.
[7] Soyeb Pathan, Anjali Patel,et al. Solvent free clean selective oxidation of alcohols catalyzedby mono transition metal (Co, Mn, Ni)-substituted Keggin-phosphomolybdates using hydrogenperoxide [J].Applied Catalysis A: General,2013,459,59–64.
[8] Yang Y Y, Xu L, Li F Y,et al. pH-dependent assembly of1D–2D structures based on both{V10O28} and [NiMo46O24H6]units: Synthesis, structure and magnetic properties [J]. Inorg ChemComm,2013,33,142–146.
[9] Guo J, Yang J, Ma J F,et al. Two new polyoxometalate-templated supramolecular compoundsconstructed by a new tridentate ligand2,4,6-tris[1-(4-oxidroxypyridinium)-ylmethyl]-mesitylene[J]. Inorganica ChimicaActa,2013,400,51–58.
[10] Shi S Y, Teng H H, Chang L M,et al. New compounds constructed from bi-antimony cappedKeggin polyoxoanions and different coordination fragments [J]. Inorganica ChimicaActa,2013,399,172–176.
[11]BROWNI ALTERMATTD.Bond-valence parameters obtained from asystematic analysis ofthe inorganic crystal structure databade［J］.ActaCryst，1985，41B：244-247.
[12] Sadakane M, Steckhan E, Electrochemical Properties of Polyoxometalates asElectrocatalysts[J]. Chem Rev,1998,98:219-237.
[1] Li L, Zhang S Q, Xu L J,et al. An Intensely Luminescent Metal Organic Framework Based ona Highly Light-Harvesting Dyclo-Metalated Iridium(III) Unit Showing Effective Detection ofExplosives [J]. Inorg. Chem.2013,52,1232312325.
[2] Yan Y, Du P, Ma J F,et al. A Series of Coordination Polymers Constructed by Flexible4Substituted Bis(1,2,4-triazole) Ligands and Polycarboxylate Anions:Syntheses, Structures, andPhotoluminescent Properties [J]. Cryst. Growth Des.2013,13,47814795.
[3] Michele R. Chierotti, Andrea Rossin, Roberto Gobetto,et al. Interaction between a Transition-Metal Fluoride and a Transition-Metal Hydride: Water-Mediated Hydrofluoric Acid EvolutionFollowing Fluoride Solvation [J]. Inorg. Chem.2013,52,1261612623.
[4] Petri Seppala,Enrique Colacio, Antonio J. Mota,et al. Structural Diversity due to AminoAlcohol Ligands Leading to Rare μ4Hydroxo-Bridged Tetranuclear and “Bicapped Cubane”Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study [J].Inorg. Chem.2013,52,1109611109.
[5] Pau Díaz-Gallifa,Oscar Fabelo, Jorge Pasan,et al. Synthesis, Crystal Structure and MagneticCharacterization of a Series of CuII LnIIIHeterometallic(Ln=La, Ce, Pr, Nd and Sm) MetalOrganic Compounds with an Unusual Single Crystal to Single Crystal Phase Transition [J].Cryst.Growth Des.,2013,13,47354745.
[6] Huang K B, Chen Z F, Liu Y C,et al. Copper(II/I) complexes of5-pyridin-2-yl-[1,3]dioxolo
[4,5-g] isoquinoline: Synthesis, crystal structure, antitumor activity and DNA interaction [J].European Journal of Medicinal Chemistry,2013,70,640648.
[7] Chandan Adhikary, Sourajit Banerjee, Sandra Ianelli,et al. Copper(II) azide complexes withNNO donor ligands: Syntheses, structure, catalysis and biological studies [J].Polyhedron,2013,65,48–53.
[8] Elena K. Beloglazkina, Alexander G. Majouga, Andrei V. Mironov,et al. Synthesis, X-raycrystallography and electrochemistry of three novel copper complexes with imidazole-containinghydantoin and thiohydantoins [J]. Polyhedron,2013,63,15–20.
[9] Lu H H, Romain Gautier, Kenneth R. Poeppelmeier,et al. Nonlinear Active Materials: AnIllustration of Controllable Phase Matchability [J]. J. Am. Chem. Soc.2013,135,1194211950.
[10] Romain Gautier and Kenneth R. Poeppelmeier,et al. Alignment of Acentric Units in InfiniteChains: A “Lock and Key” Model [J].Cryst. Growth Des.2013,13,40844091.
[11] P.Halasymani, C. L.Stern,M.J.Willis, et al., Inorg.Chem.[J],1996,35:1367-1371.
[12N.G.Furmanova,M.Kh.Rabadanov,M.S.Fonar, et al., Kristallografiya[J],2008,53:273.
[13] JIN Su-Rong(靳素荣),ZHANG Lian-Meng(张联盟),ZHAO Wei-Feng(赵卫峰), eta1..Journal of Wuhan University of Technology (武汉理工大学学报)[J],2005,27(4):2-3
[14] Norquist A. J., Welk M. E., Stern C. L., et al., Chem. Mater.[J],2000,12:1905-1909
[15]Gao S.,Liu J. W.,Huo L.H.,et a1.,Inorg.Chem.Commun.[J],2005,8:361-364