以多金属氧酸盐作为基本建筑单元构筑新颖的杂多钨酸盐化合物
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摘要
本论文运用分子设计和分子工程思想对多金属钨酸盐无机建筑单元进行组装、复合、杂化，构筑结构可塑、性能优异的新型杂化化合物。研究这类化合物的合成条件及规律，分析网络所属的拓扑类型，考察分子间作用力，过渡金属离子，配体的几何构型，辅助配体对于整个结构的影响等规律，探究分子自组装原理，探索新类型的拓扑结构，推测新型新结构的形成、以及新物质结构和性能间的关系。
利用常规合成技术或水热合成，通过利用多金属氧酸盐建筑单元的方法，水溶液中进行分子间自组装合成了10种新型的以多金属氧酸盐为建筑块的无机有机骨架化合物，通过元素分析，IR，XRPD，TG和单晶X-射线衍射对晶体结构进行了表征，对化合物的热稳定性、磁学特性和电化学性质进行了初步研究。
1．以Keggin结构的多钨酸盐作为基本建筑单元，通过有机配体，过渡金属修饰或连接，构筑新颖的无机有机杂化化合物。构的多金属氧酸盐建筑单元间通过稀土配合物的共价连接形成具有扩展结构的化合物。将孤立的Keggin结构多金属氧酸盐簇连接起来构筑具有扩展结构的化合物，不仅可以丰富多金属氧酸盐的结构化学，所得到的化合物具有不同于孤立结构的化学特性，在固体材料领域有着很好的应用前景。
K[Cu(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (1)
K[Mn(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (2)
化合物1和2都是以Keggin型的杂多磷钨酸盐为基本建筑单元，通过M(phen)_2进行支撑，再由碱土金属K作为连接单元，扩展形成的一维链状化合物。
2．利用缺位型的多钨酸盐，通过过渡金属，稀土以及有机配体对其进行修饰或连接，构筑新颖的化合物。由于稀土原子有着极高的配位数和多样的配位方式，将稀土原子引入缺位型的多金属氧酸盐中，可以得到更多新颖的结构，Zn原子等具有优秀发光特性的原子引入，使得多酸可以具有较优秀的荧光特性。同时，由于过渡金属原子的存在，化合物可能还具有优异的磁性质。
K_4LaH[As_2W_(20)CuO_(67)(H_2O)_3]Cl_2·22．5H_2O (3)
Na_2[Cu(en)]_5[Ce_2(AsW_(11)O_(39))_4]·19H_2O (4)
K_2Na_2(NH_4)_(18)[(VO)(SO)(As_4W_(40)O_(140))]·30H_2O (5)
[Zn(phen)_2]_2[Zn_6(phen)_2(AsW_9O_(33))_2] (6)
K_(11)H_2Zn[(AsW_9O_(33))_2(ZnCl)_6]Cl·27H_2O (7)
化合物3是利用夹心型化合物[As_2W_(20)CuO_(67)(H_2O)_3]~(8-)作为基本建筑单元，在水溶液中进行反应，将La原子引入从而得到新颖的3d-4f型的化合物。化合物4则是利用{AsW_9O_(33)}作为基本建筑单元，利用水热的方法得到的，利用稀土原子将2个{AsW_(11)O_(39)}片断进行连接，同时5个[Cu(en)]分别的配位到多酸骨架上，形成高纬的拓展结构。在化合物5中，我们成功的将{VO_5}和{SO_3}修饰到{As_4W_(40)O_(140)}建筑单元中。化合物6和7，是2个利用{AsW_9O_(33)}作为基本建筑单元得到的新颖的夹心型化合物，化合物中的2个Zn6簇是从未被报道过的。并且，这也是首次将高核的锌簇引入到多酸中来，并使化合物具有优秀的荧光性质。
3．利用[As_2W_(19)O_(67)(H_2O)]~(14-)作为前驱体，在水溶液中进行自组装合成新型的高核多砷钨酸盐簇化合物。绝大多数大型的多钨酸盐化合物是通过使用不同的建筑单元由‘自下而上’控制的方法得到。在合成大型多钨酸盐化合物中，我们比较关注的是一类砷钨酸盐的建筑单元例如[AsW_9O_(33)]~(9-)和[As_2W_(19)O_(67)(H_2O)]~(14-)，因为对比其他类型的建筑单元，As~Ⅲ原子具有一对孤对电子，这就使其不容易形成饱和结构并且更容易出现新颖的连接方式。
K_8Na_4[(H_2O)As_4W_(19)O_(70)]·21．5H_2O (8)
K_3Na_(22)[{W_4O_9(H_2O)_2}{As_2W_(19)O_(67)(H_2O)}_2]．14H_2O (9)
K_(10)Na_(10)[(W_(13)O_(33))(H_2O)_6(OH)_4(AsW_9O_(33))_4O_(29)]·50H_2O (10)
化合物8-10都是以[As_2W_(19)O_(67)(H_2O)]~(14-)作为基本建筑单元，通过常规方法在水溶液中得到的。化合物8中，我们首次将一个{As_2O}片断引入到[As_2W_(19)O_(67)(H_2O)]~(14-)中，得到了一个新颖的夹心型化合物。化合物9，10则是2个新颖的高核砷钨酸盐簇，到目前位置，这类纯粹的砷钨酸盐高核化合物还很少被报道。
以上这些化合物都表现出优异的热稳定性，化合物10的电化学性质和对亚硝酸根的电催化活性，可望成为一种新型的复合型功能材料。
The aim of this thesis is the synthesis of new framework compounds on the basis ofpolyoxovanadates.The study on synthetic conditions and rules for these new compounds,topological analyses,and the exploration of relationships between structures and propertiesfor these new compounds are also carried out.Twelve new compounds have been synthesizedon the basis of hydrothermal technique and/or mixed solventthermal synthesis methods andstructurally characterized by elemental analyses,IR,XRPD,TG and single crystal X-raydiffractions.The thermal stabilities,magnetic properties and electrochemical activities ofthese compounds have been studied.
1.Two new compounds have been hydrothermally synthesized by virtue of transition metalions and phosphorus-tungstate oxides with the same configurations:
K[Cu(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (1)
K[Mn(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (2)
Both compound 1 and 2 are based on Keggin type polyoxometalate {PW_(12)O_(40)} whichrepresent the first examples containing one-dimensional chain by alkaline metal-bridgedbisupporting polyoxoanion units.
2.To construct novel polyoxoanion clusters,based on the lacunary polyoxometalate asprecursor and decoration with transition metal,rare earth atoms and organicfragments.Because of theirs diversiform coordination environments,higher oxidation statesand stronger coordination capacity of lanthanide ions,we were trying to import the rare earthions,transiton metal ions and small molecule to the polyoxoanoin building blocks,on thechance of largely impove the properties of such polyoxoanions.At the same time,this class ofpolyoxoanion which contains more than one transition metal ions such as Cu,Fe,Co,Ni,Znetc.,maybe exhibiting excellent magnetic property luminesce property and photovoltage.
K_4LaH [As_2W_(20)CuO_(67)(H_2O)_3]Cl_2·22.5 H_2O (3)
Na2 [Cu(en)]_5 [Ce_2(AsW_(11)O_(39))_4]·19H_2O (4)
K_2Na_2(NH_4)_(18)[(VO)(SO)(As_4W_(40)O_(140))]·30H_2O (5)
[Zn (phen)_2]_2[Zn_6(phen)_2(AsW_9O_(33))_2] (6)
K_(11)H_2Zn [(AsW_9O_(33))_2(ZnCl)_6] Cl·27H_2O (7)
Compound 3 is an novel sandwich-type polyoxoanion construct of an La atom froming anovel 3d-4f structure.Compound 4 and 5 was sysnithized through hydrothermal technique.The two {AsW_(11)} units which connected through rare earth atoms and five [Cu(en)]fragments linked to the polyoxanions framework respectively to construct a 2-D extendedstructures.In compound 6,we were successful imported the {VOs} and a {SO_3} units to the {As_4W_(40)} fragment.Compound 7 and 8 were two new sandwich-type polyoxoanions whichcontain two novel six-nucleus clusters and have never been reported.This was firstly toimport highly Zn clusters to the polytungstoarsenate.
3.To construct highly-nucleus polytungstoarsenate clusters based on [As_2W_(19)O_(67)(H_2O)]~(14-)unit by using the strategy of self-assembly in solution.As we know,most nanosized POMclusters were prepared via the“bottom-up”control of aggregation process to get the finalhuge aggregates In synthesition of huge polytungstoarsenate,the building blocks such as{AsW_9}and {As_2W_(19)} paid more attentions because the As~Ⅲhave a alone pair of electronswhich lead this class of building blocks difficult to form saturated structure.This will make achance to form novel connect fashion and new structues.
K_8Na_4 [(H_2O)As_4W_(19)O_(70)]·21.5H_2O (8)
K_3Na_(22)[{W_4O_9(H_2O)_2} {As_2W_(19)O_(67)(H_2O)}_2].14H_2O (9)
K_(10)Na_(10)[(W_(13)O_(33))(H_2O)_6(OH)_4(AsW_9O_(33))_4O_(29)]·50H_2O (10)
Compound 9 and 10were all obtained based on the {As2W19} as the precursor andself-assembly in the solution.In compound 9,we firstly import the {As_2O} fragment to the[As_2W_(19)O_(67)(H_2O)]~(14-) and got a novel sandwich-type compound.Compound 10 is the novelhigh-nucleus polytungstoarsenates and this kinds of pure polytungstoarsenates had rare bereported till now.
利用常规合成技术或水热合成，通过利用多金属氧酸盐建筑单元的方法，水溶液中进行分子间自组装合成了10种新型的以多金属氧酸盐为建筑块的无机有机骨架化合物，通过元素分析，IR，XRPD，TG和单晶X-射线衍射对晶体结构进行了表征，对化合物的热稳定性、磁学特性和电化学性质进行了初步研究。
1．以Keggin结构的多钨酸盐作为基本建筑单元，通过有机配体，过渡金属修饰或连接，构筑新颖的无机有机杂化化合物。构的多金属氧酸盐建筑单元间通过稀土配合物的共价连接形成具有扩展结构的化合物。将孤立的Keggin结构多金属氧酸盐簇连接起来构筑具有扩展结构的化合物，不仅可以丰富多金属氧酸盐的结构化学，所得到的化合物具有不同于孤立结构的化学特性，在固体材料领域有着很好的应用前景。
K[Cu(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (1)
K[Mn(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (2)
化合物1和2都是以Keggin型的杂多磷钨酸盐为基本建筑单元，通过M(phen)_2进行支撑，再由碱土金属K作为连接单元，扩展形成的一维链状化合物。
2．利用缺位型的多钨酸盐，通过过渡金属，稀土以及有机配体对其进行修饰或连接，构筑新颖的化合物。由于稀土原子有着极高的配位数和多样的配位方式，将稀土原子引入缺位型的多金属氧酸盐中，可以得到更多新颖的结构，Zn原子等具有优秀发光特性的原子引入，使得多酸可以具有较优秀的荧光特性。同时，由于过渡金属原子的存在，化合物可能还具有优异的磁性质。
K_4LaH[As_2W_(20)CuO_(67)(H_2O)_3]Cl_2·22．5H_2O (3)
Na_2[Cu(en)]_5[Ce_2(AsW_(11)O_(39))_4]·19H_2O (4)
K_2Na_2(NH_4)_(18)[(VO)(SO)(As_4W_(40)O_(140))]·30H_2O (5)
[Zn(phen)_2]_2[Zn_6(phen)_2(AsW_9O_(33))_2] (6)
K_(11)H_2Zn[(AsW_9O_(33))_2(ZnCl)_6]Cl·27H_2O (7)
化合物3是利用夹心型化合物[As_2W_(20)CuO_(67)(H_2O)_3]~(8-)作为基本建筑单元，在水溶液中进行反应，将La原子引入从而得到新颖的3d-4f型的化合物。化合物4则是利用{AsW_9O_(33)}作为基本建筑单元，利用水热的方法得到的，利用稀土原子将2个{AsW_(11)O_(39)}片断进行连接，同时5个[Cu(en)]分别的配位到多酸骨架上，形成高纬的拓展结构。在化合物5中，我们成功的将{VO_5}和{SO_3}修饰到{As_4W_(40)O_(140)}建筑单元中。化合物6和7，是2个利用{AsW_9O_(33)}作为基本建筑单元得到的新颖的夹心型化合物，化合物中的2个Zn6簇是从未被报道过的。并且，这也是首次将高核的锌簇引入到多酸中来，并使化合物具有优秀的荧光性质。
3．利用[As_2W_(19)O_(67)(H_2O)]~(14-)作为前驱体，在水溶液中进行自组装合成新型的高核多砷钨酸盐簇化合物。绝大多数大型的多钨酸盐化合物是通过使用不同的建筑单元由‘自下而上’控制的方法得到。在合成大型多钨酸盐化合物中，我们比较关注的是一类砷钨酸盐的建筑单元例如[AsW_9O_(33)]~(9-)和[As_2W_(19)O_(67)(H_2O)]~(14-)，因为对比其他类型的建筑单元，As~Ⅲ原子具有一对孤对电子，这就使其不容易形成饱和结构并且更容易出现新颖的连接方式。
K_8Na_4[(H_2O)As_4W_(19)O_(70)]·21．5H_2O (8)
K_3Na_(22)[{W_4O_9(H_2O)_2}{As_2W_(19)O_(67)(H_2O)}_2]．14H_2O (9)
K_(10)Na_(10)[(W_(13)O_(33))(H_2O)_6(OH)_4(AsW_9O_(33))_4O_(29)]·50H_2O (10)
化合物8-10都是以[As_2W_(19)O_(67)(H_2O)]~(14-)作为基本建筑单元，通过常规方法在水溶液中得到的。化合物8中，我们首次将一个{As_2O}片断引入到[As_2W_(19)O_(67)(H_2O)]~(14-)中，得到了一个新颖的夹心型化合物。化合物9，10则是2个新颖的高核砷钨酸盐簇，到目前位置，这类纯粹的砷钨酸盐高核化合物还很少被报道。
以上这些化合物都表现出优异的热稳定性，化合物10的电化学性质和对亚硝酸根的电催化活性，可望成为一种新型的复合型功能材料。
The aim of this thesis is the synthesis of new framework compounds on the basis ofpolyoxovanadates.The study on synthetic conditions and rules for these new compounds,topological analyses,and the exploration of relationships between structures and propertiesfor these new compounds are also carried out.Twelve new compounds have been synthesizedon the basis of hydrothermal technique and/or mixed solventthermal synthesis methods andstructurally characterized by elemental analyses,IR,XRPD,TG and single crystal X-raydiffractions.The thermal stabilities,magnetic properties and electrochemical activities ofthese compounds have been studied.
1.Two new compounds have been hydrothermally synthesized by virtue of transition metalions and phosphorus-tungstate oxides with the same configurations:
K[Cu(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (1)
K[Mn(phen)_2(H_2O)]_2[PW_(12)O_(40)]·2H_2O (2)
Both compound 1 and 2 are based on Keggin type polyoxometalate {PW_(12)O_(40)} whichrepresent the first examples containing one-dimensional chain by alkaline metal-bridgedbisupporting polyoxoanion units.
2.To construct novel polyoxoanion clusters,based on the lacunary polyoxometalate asprecursor and decoration with transition metal,rare earth atoms and organicfragments.Because of theirs diversiform coordination environments,higher oxidation statesand stronger coordination capacity of lanthanide ions,we were trying to import the rare earthions,transiton metal ions and small molecule to the polyoxoanoin building blocks,on thechance of largely impove the properties of such polyoxoanions.At the same time,this class ofpolyoxoanion which contains more than one transition metal ions such as Cu,Fe,Co,Ni,Znetc.,maybe exhibiting excellent magnetic property luminesce property and photovoltage.
K_4LaH [As_2W_(20)CuO_(67)(H_2O)_3]Cl_2·22.5 H_2O (3)
Na2 [Cu(en)]_5 [Ce_2(AsW_(11)O_(39))_4]·19H_2O (4)
K_2Na_2(NH_4)_(18)[(VO)(SO)(As_4W_(40)O_(140))]·30H_2O (5)
[Zn (phen)_2]_2[Zn_6(phen)_2(AsW_9O_(33))_2] (6)
K_(11)H_2Zn [(AsW_9O_(33))_2(ZnCl)_6] Cl·27H_2O (7)
Compound 3 is an novel sandwich-type polyoxoanion construct of an La atom froming anovel 3d-4f structure.Compound 4 and 5 was sysnithized through hydrothermal technique.The two {AsW_(11)} units which connected through rare earth atoms and five [Cu(en)]fragments linked to the polyoxanions framework respectively to construct a 2-D extendedstructures.In compound 6,we were successful imported the {VOs} and a {SO_3} units to the {As_4W_(40)} fragment.Compound 7 and 8 were two new sandwich-type polyoxoanions whichcontain two novel six-nucleus clusters and have never been reported.This was firstly toimport highly Zn clusters to the polytungstoarsenate.
3.To construct highly-nucleus polytungstoarsenate clusters based on [As_2W_(19)O_(67)(H_2O)]~(14-)unit by using the strategy of self-assembly in solution.As we know,most nanosized POMclusters were prepared via the“bottom-up”control of aggregation process to get the finalhuge aggregates In synthesition of huge polytungstoarsenate,the building blocks such as{AsW_9}and {As_2W_(19)} paid more attentions because the As~Ⅲhave a alone pair of electronswhich lead this class of building blocks difficult to form saturated structure.This will make achance to form novel connect fashion and new structues.
K_8Na_4 [(H_2O)As_4W_(19)O_(70)]·21.5H_2O (8)
K_3Na_(22)[{W_4O_9(H_2O)_2} {As_2W_(19)O_(67)(H_2O)}_2].14H_2O (9)
K_(10)Na_(10)[(W_(13)O_(33))(H_2O)_6(OH)_4(AsW_9O_(33))_4O_(29)]·50H_2O (10)
Compound 9 and 10were all obtained based on the {As2W19} as the precursor andself-assembly in the solution.In compound 9,we firstly import the {As_2O} fragment to the[As_2W_(19)O_(67)(H_2O)]~(14-) and got a novel sandwich-type compound.Compound 10 is the novelhigh-nucleus polytungstoarsenates and this kinds of pure polytungstoarsenates had rare bereported till now.
引文
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