多金属氧酸盐论文：多金属氧酸盐Keggin结构稀土离子配合物Cu(ⅠⅡ)配合物晶体结构

1、物Cu(I/II)配合物晶体结构【中文摘要】本论文采用饱和型及单缺位Keggin杂多阴离子作为基本建筑单元，在水热及常温条件下，合成了八种迄今未见报道的稀土及过渡金属离子配合物，利用元素分析、IR、TG和单晶X-射线技术对其组成和结构进行了表征，对部分配合物进行了电化学及光催化产氢的研究。1.稀土离子Ce(皿)丄a(H),配体为2,6-二羧基吡啶(pdc),水热合成了四种Keggin杂多阴离子配合物：H2H2O1H22H2O2H42H2O3H42H2O4配合物1通过Ce3+与pdc配体桥连形成2D层状结构,3-作为建筑块将2D金属有机配体层桥连进一步形成3D柱撑型配合物；配合物2是由两个游离的

2、2+片段通过氢键与3-作用形成0维结构;配合物3,4通过稀土金属与pdc配体形成3D有机框架,5-镶嵌在有机框架中。另外，对配合物1进行电化学及光催化产氢性质的研究，发现配合物1具有光催化产氢活性，产氢速率为3.4卩molh-1。2.将单缺位取代型8-杂多酸阴离子和稀土离子Sm3+在70C,pH为5.15含有少量DMS啲水溶液中反应，合成出一种1D结构的多金属氧酸盐配合物：2(OH2219H2O5配合物5中缺位8-多阴离子通过Sm3连接形成1D链结构,Sm3+与配体DMS形成的二聚体Sm(DMSQ(H2O与多酸上的端氧桥连进一步扩展为1D双链结构。3.利用相同的4-多酸阴离子，过渡金属Cu2+

3、及配体4,4'-bipy,在水热条件下合成出三种配合物：2(HSiW12O40)H2O62(H2SiW12O40)7(SiW12O40)8在配合物6中,4-多酸阴离子通过一维阳离子聚合链Cu(4,4-bipy)+连接形成2D层状结构；在配合物7中Cu(4,4-bipy)+与4-桥连形成1D轨道型结构；在化合物8中,Cu2+,4,4-bipy,CH3COO-以及4-多酸阴离子构筑的2D金属有机配体层通过氢键作用形成沿c轴以a,b,a,b模式排列的3D结构；同时对化合物6,7,8进行了电化学性质的研究。【英文摘要】Inthisthesis,eightcompoundsbasedonsatu

4、ratedandmonovacantKegginpolyoxoanionclustersasbuildingblockshavebeensynthesizedunderhydrothermalandnormaltemperatureconditions,andcharacterizedbyelementalanalysis,IR,TGandX-raysinglecrystaldiffraction.ThephotocatalyticH2evolutionandtheelectrochemistryhavebeenstudiedforsomeofthem.1.FourIanthanidecomp

5、lexeshavebeensynthesizedhydrothermally:HCe(H2O52Ce(pdc)2(H2O4Ce(pdc)3(PW12O40)2H2O1HCe(pdc)(H2O62PMo12O402H2O2HLa(H2O4(pdc)4BW12O402H2O3HCe(H2O4(pdc)4BW12O402H2O4Complex1exhibits2DlayerstructureconstructedbyCe3+andpdcligands.ThelayersarepillaredbyKegginanions.Complex2exhibitsa0DstructurebuildfromPMo

6、12O403-anionsandCe(pdc)(H2O62+units.Incomplexes3and4,a3Dorganicframeworkisconstructedbyrare-earthionsandpdcandBW12O405-areembeddedintheorganicframework.ElectrochemistryandphotocatalyticH2evolutionhavebeenstudiedforcomplexesItisfoundthatcomplexe1exhibitsphotocatalyticactivityforH2evolutionattherateof

7、3.4卩molh-1.2.One1DSm3+complexhasbeensynthesizedusingmonovacantKegginpolyoxoanionclusters,organicsolventDMSOandrare-earthionsat70CandpH=5.15:Sm2(H2O9(DMSQ2(OH2Sm(H2O3(DMSQSiW11O39)219H2O5lncomplex5,a1Dchain-likestructureisformedbySm3+andSiW11O398-,thena2Ddoublechain-likestructureisconstructedbySm(DMS

8、Q(H2Odimersandthe1Dchainstructure.3.ThreeCu(H/I)complexeshavebeenhydrothermallysynthesizedusingSiW12O404-anions,4,4'-bipyandmetalCu2+ions:Cu(4,4'-bipy)2(HSiW12O4O)Cu(4,4'-bipy)-H2O6Cu(4,4'-bipy)2(H2SiW12O40)7H2Cu2(4,4'-bipy)3(CH3CQO2(SiW12O40)8Incomplex6,one-dimensionalcationicpolymerchains,Cu(4,4'-bipy)+,linkSiW12O404-anionstoforma2Dlayerstructure.Incomplex7,a1Drail-likestructureisconstructedfromCu(4,4-bipy)+andSiW12O404-anions.Incomplex8,a2Dlayerstructure