多钨铋酸盐和稀土、碱土金属的配位组装、多维结构和性质研究
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摘要
本论文采用常规方法设计合成了13个具有多维结构的多钨铋酸盐和稀土、碱土金属的化合物。并通过红外、紫外－可见光谱、元素分析、热重和单晶X-射线对晶体结构进行了表征，并对化合物的荧光性质、磁学性质和表面光电压性质进行了研究。
1．以Na12[Bi_2W_(22)O_(74)(OH)_2]·44H_2O(缩写为：{Bi_2W_(22)})、Na_9[BiW_9O_(33)]·16H_2O(缩写为：{BiW~(3+)9})，稀土离子(Pr_~(3+)，Nd，La~(3+)和Ce~(3+))和Na_2CO_3为原料合成了四例被多钨铋酸盐包裹稀土离子的化合物1-4：
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Pr_3(H_2O)6CO_3)]·95H_2O (1)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Nd3(H_2O)6CO_3)]·91H_2O (2)
Na_(20)H_2[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(La3(H_2O)6CO_3)]·73H_2O (3)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Ce3(H_2O)6CO_3)]·85H_2O (4)
单晶分析揭示化合物1-4的结构是相同的。呈三角形分布的三个a-B-{BiW_9}单元通过一个[{Ln_3(H_2O)_6CO_3}]7+{Ln=Pr_~(3+)(1), Nd~(3+)(2), La~(3+)(3), Ce~(3+)(4)}单元相连接，并且通过一个[{Bi_6(3-O)_4(2-OH)_3}]~(7+)单元和一个六配体的W原子与第四个a-B-{BiW_9}单元相连接。研究了化合物1的荧光性质，结果表明其可以作为潜在的荧光材料，磁性研究表明化合物1和2中存在着反铁磁性相互作用。
2.在常规水溶液体系中采用{Bi_2W_(22)}、{BiW_9}和ErCl3为原料合成了化合物5：
Na_(4.5)H_(5.5)[Bi_2W_(21)Er(H_2O)3(OH)]·40H_2O (5)
化合物5中的两个[Bi_2W_(21)O72Er(H_2O)3(OH)]10-(简称为{Bi_2W_(21)Er})建筑单元通过两个Er–O–W连接形成一个中心对称的二聚体，并且此二聚体通过Na+离子相连形成二维平面结构。磁性研究表明化合物5中存在着反铁磁性的相互作用。
3.在常规水溶液体系中以{Bi+2W_(22)}、{BiW_9}和碱土金属离子(Ca2, Sr~(2+)和Ba~(2+))为原料，得到了四个基于仲钨酸盐-B离子[H10-2W_(12)O_(42)]和碱土金属离子的全无机多维多酸化合物6-9。
Ca2Na6[H_2W_(12)O_(42)]·30H_2O (6)
Sr_4H_2[H_2W_(12)O_(42)]·26H_2O (7)
Sr_4Na_2[H_2W_(12)O_(42)]·30H_2O (8)
Ba_4Na_2[H_2W_(12)O_(42)]·29.5H_2O (9)
反应中的起始原料{Bi0-2W_(22)}起到了重要作用，[H12W_(12)O_(42)]构筑单元是由{Bi_2W_(22)O_(74)(OH)_2}前驱体分解而形成的，从而避免了沉淀的生成。其中化合物7代表了第一例基于[H12W_(12)O_(42)]0-构筑单元和仅采用碱土金属离子连接的全无机三维结构。表面光电压测试表明化合物6-9都主要显示p型半导体性质，可能作为潜在的光催化剂和光电转换材料。化合物6-9的固体漫反射紫外-可见光谱显示出了它们具有较大的能带差的半导体性质。化合物6-9的荧光光谱与CaWO_4、SrWO_4和BaWO_4的荧光光谱非常相似，这表明化合物6-9可以像CaWO_4一样作为潜在的激光和荧光材料。
4.在常规水溶液体系中以Na_(10)[Bi_2W_(20)Co_2O_(70)(H_2O)6]·41H_2O (缩写为：{Bi_2W_(20)Co_2})、{BiW_9}和碱土金属离子(Ca~(2+), Sr~(2+)和Ba~(2+))为原料，得到了四个以多钨铋酸盐{Bi_2W_(20)Co_2}和碱土金属离子的多维配合物10-13。
Ca2Na_2H_4[Bi_2W_(20)Co_2O_(70)(H_2O)6]·41H_2O (10)
Sr_4Na_2[Bi_2W_(20)Co_2O_(70)(H_2O)6]·35H_2O (11)
Sr_3H_4[Bi_2W_(20)Co_2O_(70)(H_2O)6]·38H_2O (12)
Ba_4H_2[Bi_2W_(20)Co_2O_(70)(H_2O)6]·39.5H_2O (13)
在相似的反应体系中用{Bi_2W_(22)Co_2}代替{Bi_2W_(22)}时，反应过程中并没有分解过程发生。化合物13代表了第一例杂多阴离子与Ba~(2+)形成的三维网络结构。磁性测试表明化合物10-13中邻近的Co_~(2+)离子之间存在着弱的反铁磁性相互作用。
Thirteen new compounds based on tungstobismuthates and lanthanide cations,alkaline-earth metal cations have been synthesized via conventional method. Thesecompounds were structurally characterized by IR, UV-Vis, elemental analyses, TG and singlecrystal X-ray diffractions. The photoluminescence, magnetic property and surfacephotovoltage property of the compounds have been discussed.
1. The reaction of Na12[Bi_2W_(22)O_(74)(OH)_2]·44H_2O(abbr.{Bi_2W_(22)}),Na_9[BiW_9O_(33)]·16H_2O (abbr.{BiW_9}), lanthanide chloride(Pr_~(3+)，Nd~(3+)，La~(3+)和Ce~(3+)) andNa_2CO_3in aqueous solution resulted in the four unprecedented giantlanthanide-tungstobismuthate compounds1-4.
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Pr_3(H_2O)6CO_3)]·95H_2O (1)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Nd3(H_2O)6CO_3)]·91H_2O (2)
Na_20H_2[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(La3(H_2O)6CO_3)]·73H_2O (3)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Ce3(H_2O)6CO_3)]·85H_2O (4)
The result of Single-crystal X-ray diffraction analysis reveals that the polyanions of thefour complexes are isomorphic. A trigonal arrangement of three lacunary a-B-{BiW_9}fragments is linked by one [{Ln+3(H_2O)6CO_3}]7+{Ln=Pr_~(3+)(1), Nd3(2), La~(3+)(3), Ce~(3+)(4)}unit. This assembly is connected to the fourth a-B-{BiW_9} fragment by means of one[{Bi_6(3-O)_4(72-OH)3}]+polyoxo cation and one additional six-coordinate tungsten atom.The luminescent property of1was characterized. This result suggests that the compound1may be a good candidate for fluorescent materials. Magnetic investigation revealed that theweak antiferromagnetic interaction between the neighboring metal centres are responsible forthe magnetic properties of1and2.
2. The reaction of {Bi_2W_(22)},{BiW_9} and ErCl3in aqueous solution resulted in acompound5:
Na_(4.5)H_(5.5)[Bi_2W_(21)Er(H_2O)3(OH)]·40H_2O (5)
A centrosymmertric dimer in the compound5is built from two[Bi_2W_(21)O72Er(H_2O)3(OH)]10-fragments by means of two Er–O–W link, The dimer is leadedto the formation of a2D network connected by Na anions. The magnetic investigation on5reveal weak antiferromagnetic interactions between the magnetic centers.3. Four all-inorganic multidimensional polyoxometalate compounds6-9based on theparadodecatungstate-B anions [H_2W_(12)O_(42)]10-and alkaline-earth metal have been isolated bythe reaction of {Bi_2W_(22)},{BiW_9}, and alkaline-earth metal ions(Ca~(2+), Sr~(2+)and Ba~(2+)) inaqueous solution.
Ca2Na6[H_2W_(12)O_(42)]·30H_2O (6)
Sr_4H_2[H_2W_(12)O_(42)]·26H_2O (7)
Sr_4Na_2[H_2W_(12)O_(42)]·30H_2O (8)
Ba_4Na_2[H_2W_(12)O_(42)]·29.5H_2O (9)
The starting materials of {Bi_2W_(22)} precursor play an important role in the synthesisreaction, in which the [H_2W_(12)O_(42)]~(10-)anion slowly arose from {Bi_2W_(22)} precursor so as toavoid the formation of precipitation. The compound7represents the first example of3Dall-inorganic frameworks in which the paradodecatungstate-B [H12W_(12)O_(42)]~(10-)anions werelinked by only alkaline-earth metal cations. The surface photovoltage spectra (SPS) andelectric field-induced surface photovoltage spectra (EFISPS) demonstrate that compounds6–9should be of p-type semiconductors, suggesting the possibility to become new photocatalysisand light-to-electricity conversion materials. The reflectance spectra of the compounds6-9reveal the nature of semiconductivities with a large energy gap for compounds1–4. the PLspectra of compounds6–9are very similar to CaWO_4, SrWO_4and BaWO_4, suggesting thatcompounds6–9may find application like CaWO_4in laser and fluorescent materials.
4.The reaction of Na_(10)[Bi_2W_(20)Co_2O_70(H_2O)_6]·41H_2O(abbr.{Bi_2W_(20)Co_2}),{BiW9},alkaline-earth metal ions(Ca~(2+), Sr~(2+)and Ba~(2+)) in aqueous solution at resulted in the fourmultidimensional polyoxometalate compounds10-13based on the {Bi_2W_(20)Co_2} andalkaline-earth metal
Ca2Na_2H_4[Bi_2W_(20)Co_2O_(70)]·37H_2O (10),
Sr_4Na_2[Bi_2W_(20)Co_2O_(70)]·36H_2O (11),
Sr_3H_4[Bi_2W_(20)Co_2O_(70)]·57.5H_2O (12)
Ba_4H_2[Bi_2W_(20)Co_2O_(70)]·45.5H_2O (13)
When the {Bi_2W_(22)} precursor was replaced by {Bi_2W_(22)Co_2} with the similar synthesisroutine, decomposition process in the reaction did not happen. The compound13representsthe first example of polyanions coordinating Ba cations with the unprecedented3D networkstructure. The magnetic investigation of10-13indicate the presence of an antiferromagneticinteraction between the neighboring magnetic centers.
1．以Na12[Bi_2W_(22)O_(74)(OH)_2]·44H_2O(缩写为：{Bi_2W_(22)})、Na_9[BiW_9O_(33)]·16H_2O(缩写为：{BiW~(3+)9})，稀土离子(Pr_~(3+)，Nd，La~(3+)和Ce~(3+))和Na_2CO_3为原料合成了四例被多钨铋酸盐包裹稀土离子的化合物1-4：
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Pr_3(H_2O)6CO_3)]·95H_2O (1)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Nd3(H_2O)6CO_3)]·91H_2O (2)
Na_(20)H_2[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(La3(H_2O)6CO_3)]·73H_2O (3)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Ce3(H_2O)6CO_3)]·85H_2O (4)
单晶分析揭示化合物1-4的结构是相同的。呈三角形分布的三个a-B-{BiW_9}单元通过一个[{Ln_3(H_2O)_6CO_3}]7+{Ln=Pr_~(3+)(1), Nd~(3+)(2), La~(3+)(3), Ce~(3+)(4)}单元相连接，并且通过一个[{Bi_6(3-O)_4(2-OH)_3}]~(7+)单元和一个六配体的W原子与第四个a-B-{BiW_9}单元相连接。研究了化合物1的荧光性质，结果表明其可以作为潜在的荧光材料，磁性研究表明化合物1和2中存在着反铁磁性相互作用。
2.在常规水溶液体系中采用{Bi_2W_(22)}、{BiW_9}和ErCl3为原料合成了化合物5：
Na_(4.5)H_(5.5)[Bi_2W_(21)Er(H_2O)3(OH)]·40H_2O (5)
化合物5中的两个[Bi_2W_(21)O72Er(H_2O)3(OH)]10-(简称为{Bi_2W_(21)Er})建筑单元通过两个Er–O–W连接形成一个中心对称的二聚体，并且此二聚体通过Na+离子相连形成二维平面结构。磁性研究表明化合物5中存在着反铁磁性的相互作用。
3.在常规水溶液体系中以{Bi+2W_(22)}、{BiW_9}和碱土金属离子(Ca2, Sr~(2+)和Ba~(2+))为原料，得到了四个基于仲钨酸盐-B离子[H10-2W_(12)O_(42)]和碱土金属离子的全无机多维多酸化合物6-9。
Ca2Na6[H_2W_(12)O_(42)]·30H_2O (6)
Sr_4H_2[H_2W_(12)O_(42)]·26H_2O (7)
Sr_4Na_2[H_2W_(12)O_(42)]·30H_2O (8)
Ba_4Na_2[H_2W_(12)O_(42)]·29.5H_2O (9)
反应中的起始原料{Bi0-2W_(22)}起到了重要作用，[H12W_(12)O_(42)]构筑单元是由{Bi_2W_(22)O_(74)(OH)_2}前驱体分解而形成的，从而避免了沉淀的生成。其中化合物7代表了第一例基于[H12W_(12)O_(42)]0-构筑单元和仅采用碱土金属离子连接的全无机三维结构。表面光电压测试表明化合物6-9都主要显示p型半导体性质，可能作为潜在的光催化剂和光电转换材料。化合物6-9的固体漫反射紫外-可见光谱显示出了它们具有较大的能带差的半导体性质。化合物6-9的荧光光谱与CaWO_4、SrWO_4和BaWO_4的荧光光谱非常相似，这表明化合物6-9可以像CaWO_4一样作为潜在的激光和荧光材料。
4.在常规水溶液体系中以Na_(10)[Bi_2W_(20)Co_2O_(70)(H_2O)6]·41H_2O (缩写为：{Bi_2W_(20)Co_2})、{BiW_9}和碱土金属离子(Ca~(2+), Sr~(2+)和Ba~(2+))为原料，得到了四个以多钨铋酸盐{Bi_2W_(20)Co_2}和碱土金属离子的多维配合物10-13。
Ca2Na_2H_4[Bi_2W_(20)Co_2O_(70)(H_2O)6]·41H_2O (10)
Sr_4Na_2[Bi_2W_(20)Co_2O_(70)(H_2O)6]·35H_2O (11)
Sr_3H_4[Bi_2W_(20)Co_2O_(70)(H_2O)6]·38H_2O (12)
Ba_4H_2[Bi_2W_(20)Co_2O_(70)(H_2O)6]·39.5H_2O (13)
在相似的反应体系中用{Bi_2W_(22)Co_2}代替{Bi_2W_(22)}时，反应过程中并没有分解过程发生。化合物13代表了第一例杂多阴离子与Ba~(2+)形成的三维网络结构。磁性测试表明化合物10-13中邻近的Co_~(2+)离子之间存在着弱的反铁磁性相互作用。
Thirteen new compounds based on tungstobismuthates and lanthanide cations,alkaline-earth metal cations have been synthesized via conventional method. Thesecompounds were structurally characterized by IR, UV-Vis, elemental analyses, TG and singlecrystal X-ray diffractions. The photoluminescence, magnetic property and surfacephotovoltage property of the compounds have been discussed.
1. The reaction of Na12[Bi_2W_(22)O_(74)(OH)_2]·44H_2O(abbr.{Bi_2W_(22)}),Na_9[BiW_9O_(33)]·16H_2O (abbr.{BiW_9}), lanthanide chloride(Pr_~(3+)，Nd~(3+)，La~(3+)和Ce~(3+)) andNa_2CO_3in aqueous solution resulted in the four unprecedented giantlanthanide-tungstobismuthate compounds1-4.
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Pr_3(H_2O)6CO_3)]·95H_2O (1)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Nd3(H_2O)6CO_3)]·91H_2O (2)
Na_20H_2[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(La3(H_2O)6CO_3)]·73H_2O (3)
Na_(22)[(BiW_9O_(33))_4(WO_3){Bi_6(3-O)_4(2-OH)3}(Ce3(H_2O)6CO_3)]·85H_2O (4)
The result of Single-crystal X-ray diffraction analysis reveals that the polyanions of thefour complexes are isomorphic. A trigonal arrangement of three lacunary a-B-{BiW_9}fragments is linked by one [{Ln+3(H_2O)6CO_3}]7+{Ln=Pr_~(3+)(1), Nd3(2), La~(3+)(3), Ce~(3+)(4)}unit. This assembly is connected to the fourth a-B-{BiW_9} fragment by means of one[{Bi_6(3-O)_4(72-OH)3}]+polyoxo cation and one additional six-coordinate tungsten atom.The luminescent property of1was characterized. This result suggests that the compound1may be a good candidate for fluorescent materials. Magnetic investigation revealed that theweak antiferromagnetic interaction between the neighboring metal centres are responsible forthe magnetic properties of1and2.
2. The reaction of {Bi_2W_(22)},{BiW_9} and ErCl3in aqueous solution resulted in acompound5:
Na_(4.5)H_(5.5)[Bi_2W_(21)Er(H_2O)3(OH)]·40H_2O (5)
A centrosymmertric dimer in the compound5is built from two[Bi_2W_(21)O72Er(H_2O)3(OH)]10-fragments by means of two Er–O–W link, The dimer is leadedto the formation of a2D network connected by Na anions. The magnetic investigation on5reveal weak antiferromagnetic interactions between the magnetic centers.3. Four all-inorganic multidimensional polyoxometalate compounds6-9based on theparadodecatungstate-B anions [H_2W_(12)O_(42)]10-and alkaline-earth metal have been isolated bythe reaction of {Bi_2W_(22)},{BiW_9}, and alkaline-earth metal ions(Ca~(2+), Sr~(2+)and Ba~(2+)) inaqueous solution.
Ca2Na6[H_2W_(12)O_(42)]·30H_2O (6)
Sr_4H_2[H_2W_(12)O_(42)]·26H_2O (7)
Sr_4Na_2[H_2W_(12)O_(42)]·30H_2O (8)
Ba_4Na_2[H_2W_(12)O_(42)]·29.5H_2O (9)
The starting materials of {Bi_2W_(22)} precursor play an important role in the synthesisreaction, in which the [H_2W_(12)O_(42)]~(10-)anion slowly arose from {Bi_2W_(22)} precursor so as toavoid the formation of precipitation. The compound7represents the first example of3Dall-inorganic frameworks in which the paradodecatungstate-B [H12W_(12)O_(42)]~(10-)anions werelinked by only alkaline-earth metal cations. The surface photovoltage spectra (SPS) andelectric field-induced surface photovoltage spectra (EFISPS) demonstrate that compounds6–9should be of p-type semiconductors, suggesting the possibility to become new photocatalysisand light-to-electricity conversion materials. The reflectance spectra of the compounds6-9reveal the nature of semiconductivities with a large energy gap for compounds1–4. the PLspectra of compounds6–9are very similar to CaWO_4, SrWO_4and BaWO_4, suggesting thatcompounds6–9may find application like CaWO_4in laser and fluorescent materials.
4.The reaction of Na_(10)[Bi_2W_(20)Co_2O_70(H_2O)_6]·41H_2O(abbr.{Bi_2W_(20)Co_2}),{BiW9},alkaline-earth metal ions(Ca~(2+), Sr~(2+)and Ba~(2+)) in aqueous solution at resulted in the fourmultidimensional polyoxometalate compounds10-13based on the {Bi_2W_(20)Co_2} andalkaline-earth metal
Ca2Na_2H_4[Bi_2W_(20)Co_2O_(70)]·37H_2O (10),
Sr_4Na_2[Bi_2W_(20)Co_2O_(70)]·36H_2O (11),
Sr_3H_4[Bi_2W_(20)Co_2O_(70)]·57.5H_2O (12)
Ba_4H_2[Bi_2W_(20)Co_2O_(70)]·45.5H_2O (13)
When the {Bi_2W_(22)} precursor was replaced by {Bi_2W_(22)Co_2} with the similar synthesisroutine, decomposition process in the reaction did not happen. The compound13representsthe first example of polyanions coordinating Ba cations with the unprecedented3D networkstructure. The magnetic investigation of10-13indicate the presence of an antiferromagneticinteraction between the neighboring magnetic centers.
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