多金属氧酸盐无机有机杂化材料的水热合成和晶体结构
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摘要
金属无机有机杂化材料是通过含给电子基团的双齿或多齿有机配体(L)和一种或几种中心金属离子(M)通过配位键自组装而形成的。中心离子通常是过渡金属，具有一定的配位模式，起模板作用。有机配体具有多个配位点，起构件作用。
多钨磷酸盐无机有机杂化材料作为多金属氧酸盐无机有机杂化材料的一个重要分支，由于其丰富的结构化学及其在催化和材料领域的潜在应用而越来越受到关注。
本论文主要包括四个方面：
1．采用水热法成功合成多金属氧酸盐稀土无机有机杂化材料[Nd(PW_(11)O_(39))(H_2O)_3](H_2bpy)_2·4H_2O和Gd(bpy)_3PW_(12)O_(40)·4H_2O，知道这两种晶体是两种新材料。
2．对于杂化材料[Nd(PW_(11)O_(39))(H_2O)_3](H_2bpy)_2·4H_2O(bpy=4，4’-联吡啶)，选取0.20 mm×0.20 mm×0.10 mm的单晶，在Buker Smart APEX-CCD X射线单晶衍射仪上，用石墨单色器单色化的Mo Ka辐射(λ=0.071073nm)，在296K下收集衍射数据。在4.38°≤2θ≤60°的范围内收集到20738个衍射数据，其中独立衍射14820个。其空间群为P(-1)，属于三斜晶系，是一种单缺位的一维无机有机杂化材料。
3．对于晶体Gd(bpy)_3PW_(12)O_(40)·4H_2O，根据热重和差热分析，发现温度低于253℃的时候，晶体很稳定．根据晶体学理论和文献信息，推测其可能也是一维的无机有机杂化材料，由(PW_(12)O_(40))~(3-)连接成一维链，而bpy分子穿插在其中。
4．对两种无机有机杂化材料做了一系列的条件实验，大概得到了合成这两种无机有机杂化化合物的最佳反应条件。通过各种条件实验，确定合成第一种化合物的最佳的温度是130℃，最佳pH是6，最佳水量是10-17ml，配比为4：4：1。第二种化合物最佳的温度是140℃，最佳pH是6，最佳水量是10-17ml，配比为4：4：1。
Metal inorganic-organic hybrid materials are formed by self-assembly through coordination bonds between bidentate or multibentate organic ligands and central metal ions.The central ion, in general , is transitional metal ion with a definite coordination model, acting as template and organic ligand with many coordination sites, acting as building block.
There are tremendous activities these years in the area of inorganic-organic hybrid materials based on polyoxometalate because of their diversified structures and interesting properties, which endows these materials with applications to sorption, catalysis, electrical conductivity and solar energy conversion.
In this dissertation, there are four parts. The first part isSuccessfully synthesize inorganic-Organic hybridcompound[Nd(PW_(11) O_(39) )(H_2O_3) ](H_2bpy)_2·4H_2O and Gd(bpy)_3PW_(12) O_(40)·4H_2O,the two compounds is two new kinds of hybridmaterials.The secong part is ,through single crystal analysis,the firstcompound is deposited as one dimensional chain structure, containedprotonated ligands in the structure,and the space group is P(-1) ,belong to triclinic crystal system.The crystal is a kind of onedimensinonal monosubstituted inorganic-organic hybrid material.Thethird part is when the temperature is lower than 253℃,the crystal isstable through TG analysis. Also speculate the crystal structure of Gd(bpy)_3PW_(12) O_(40)·4H_2O based on crystal theory and information ofpapers.The crystal is also a kind of one dimensionalinorganic-organic hybrid material deposited through(PW_(12) O_(40) )~(3-),contained bpy molecules in the structure .The fourth partis test the factors affecting the outcome through conditionalexperiments. obtain the probable best condition of the synthesis ofthese two crystals. we determine that the best conditions for the firstcompound is temperature equal to 130℃,pH=6, volume of waterequal to 10-17ml, ratio of reactants equal to 4:4:1。The second istemperature equal to 140℃,pH=6, volume of water equal to10-17ml, ratio of reactants equal to 4:4:1。
多钨磷酸盐无机有机杂化材料作为多金属氧酸盐无机有机杂化材料的一个重要分支，由于其丰富的结构化学及其在催化和材料领域的潜在应用而越来越受到关注。
本论文主要包括四个方面：
1．采用水热法成功合成多金属氧酸盐稀土无机有机杂化材料[Nd(PW_(11)O_(39))(H_2O)_3](H_2bpy)_2·4H_2O和Gd(bpy)_3PW_(12)O_(40)·4H_2O，知道这两种晶体是两种新材料。
2．对于杂化材料[Nd(PW_(11)O_(39))(H_2O)_3](H_2bpy)_2·4H_2O(bpy=4，4’-联吡啶)，选取0.20 mm×0.20 mm×0.10 mm的单晶，在Buker Smart APEX-CCD X射线单晶衍射仪上，用石墨单色器单色化的Mo Ka辐射(λ=0.071073nm)，在296K下收集衍射数据。在4.38°≤2θ≤60°的范围内收集到20738个衍射数据，其中独立衍射14820个。其空间群为P(-1)，属于三斜晶系，是一种单缺位的一维无机有机杂化材料。
3．对于晶体Gd(bpy)_3PW_(12)O_(40)·4H_2O，根据热重和差热分析，发现温度低于253℃的时候，晶体很稳定．根据晶体学理论和文献信息，推测其可能也是一维的无机有机杂化材料，由(PW_(12)O_(40))~(3-)连接成一维链，而bpy分子穿插在其中。
4．对两种无机有机杂化材料做了一系列的条件实验，大概得到了合成这两种无机有机杂化化合物的最佳反应条件。通过各种条件实验，确定合成第一种化合物的最佳的温度是130℃，最佳pH是6，最佳水量是10-17ml，配比为4：4：1。第二种化合物最佳的温度是140℃，最佳pH是6，最佳水量是10-17ml，配比为4：4：1。
Metal inorganic-organic hybrid materials are formed by self-assembly through coordination bonds between bidentate or multibentate organic ligands and central metal ions.The central ion, in general , is transitional metal ion with a definite coordination model, acting as template and organic ligand with many coordination sites, acting as building block.
There are tremendous activities these years in the area of inorganic-organic hybrid materials based on polyoxometalate because of their diversified structures and interesting properties, which endows these materials with applications to sorption, catalysis, electrical conductivity and solar energy conversion.
In this dissertation, there are four parts. The first part isSuccessfully synthesize inorganic-Organic hybridcompound[Nd(PW_(11) O_(39) )(H_2O_3) ](H_2bpy)_2·4H_2O and Gd(bpy)_3PW_(12) O_(40)·4H_2O,the two compounds is two new kinds of hybridmaterials.The secong part is ,through single crystal analysis,the firstcompound is deposited as one dimensional chain structure, containedprotonated ligands in the structure,and the space group is P(-1) ,belong to triclinic crystal system.The crystal is a kind of onedimensinonal monosubstituted inorganic-organic hybrid material.Thethird part is when the temperature is lower than 253℃,the crystal isstable through TG analysis. Also speculate the crystal structure of Gd(bpy)_3PW_(12) O_(40)·4H_2O based on crystal theory and information ofpapers.The crystal is also a kind of one dimensionalinorganic-organic hybrid material deposited through(PW_(12) O_(40) )~(3-),contained bpy molecules in the structure .The fourth partis test the factors affecting the outcome through conditionalexperiments. obtain the probable best condition of the synthesis ofthese two crystals. we determine that the best conditions for the firstcompound is temperature equal to 130℃,pH=6, volume of waterequal to 10-17ml, ratio of reactants equal to 4:4:1。The second istemperature equal to 140℃,pH=6, volume of water equal to10-17ml, ratio of reactants equal to 4:4:1。
引文
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