金属-氧簇的合成、结构与性能研究
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摘要
本论文主要从事钒、钼、钨的同多及杂多金属-氧簇合物的水热合成、结构及性能研究,旨在研究金属-氧簇的多样性,在此基础上探讨它们的磁性和光学等性质。设计通过无机团簇与有机配合物的相互作用,合成系列具有结构新颖的支撑型的多金属氧酸盐(POMs)。
本文合成了六个混配型钼-钒-磷具有四帽或二帽的Keggin 结构的多金属氧酸盐。其中两个化合物是Keggin 结构的阴离子支撑两个过渡金属配合物,两个同构的阴、阳离子皆为支撑结构的多金属氧酸盐的化合物, 其中正离子是由混合钼-钒四帽Keggin 结构的簇阴离子支撑四个过渡金属配合物阳离子构成的,负离子是由混合钼-钒四帽Keggin 结构的阴离子支撑两个过渡金属配合物构成的(第三章)。合成了一个三维结构的钴钼磷酸盐和两个单钼的同多金属氧酸盐,在以[Mo_6P_4]为结构单元构筑的化合物中它是第一个同时包含四面体配位和八面体配位钴的钴钼磷酸盐(第四章)。四个单钒的同多金属氧酸盐,其中一个具有分立结构的钒酸盐带有十一个结晶水。这些水分子形成了规则的水簇,并通过氢键与簇阴离子[V_4O_(12)]_4-一起构成网络结构。两个钒-氧杂化材料是由钒氧簇和过渡金属配合物连接为二维的扩展结构,由邻菲啰啉间的π-π作用形成三维超分子结构。还有一个由无机钒氧层和有机过渡金属配合物组成的三维结构的化合物。两个砷-钒多金属氧酸盐(第五章)。三个具有镶嵌结构的钨氧簇合物,核心簇为Keggin 结构的[MW_(12)O_(40)]~(n-) (M = Co 或Ni)两边分别镶嵌一个Co(或Ni),这个镶嵌的Co(或Ni)分别与簇上的四个氧和两个其它的原子配位,其结构类型很新颖(第六章),以及一个涉及N 杂环配体原位羟化反应的异核的含混合价CuI/CuII 的化合物(第七章)。对本论文所合成的化合物进行X-射线衍射、红外、热重、顺磁及X-射线光电子能谱的结构表征。对部分化合物进行了磁学性能的测试和探讨。详细分析并阐述了上述化合物的合成条件和方法,温度、压力、浓度等对产物结构的影响,为该体系化合物的进一步研究奠定了基础。
Polyoxometalates (POMs) represent a fascinating class of inorganic chemistry with a structural variety and interesting properties, which are of use in fields as diverse as catalysis, sorption, molecular electronics, medicine, etc. A great progress in metal-oxo cluster chemistry has been study of polyoxoanion-supporting inorganic or organometallic complexes, in which Keggin unit and its derivative-supporting metal complexes is an important family. There exist two kinds of Keggin cluster-supported metal complexes. One is molecular clusters possessing discrete structures, the other is cluster polymers constructed from Keggin units as building blocks and metal complexes as bridges.
During our research for the metal-oxygen clusters, we synthesized some decorated metal-oxygen clusters, the cluster based on molybdenum-vanadium, cobalt phosphomolybdate, polyoxovanadate, polyoxotungstate and hetero-nuclear Cu'/Cu" compound involving hydroxylation of N-heterocycle ligands. On the bases of X-ray structural analyses, some compounds have been characterized by IR, XPS, ESR spectra. The thermal analyses and magnetic properties of some compounds have also been studied, which would take a role in the explorations of structures and functions for the compounds. 1. The mixed molybdenum-vanadium polyoxometalates.
The hydrothermal reactions give six novel compounds ,which consist of highly
reduced tetra or bi-capped pseudo-Keggin polyoxoanion supporting transition metal complexes, {[Co(phen)2]2-C2O4}{H2PMoVI3MoV5VIV8O44[Co(phen)2 (H2O)]2}·7H2O 1 和[Cu(phen)2]4{HPMo8VIVIV6O42[Cu(phen)]2}·2H2O 2,{[Ni(2,2’-bipy)2H2O]4 [MoV3MoVI5VIV8O40(PO4)]}{[Ni(2,2’-bipy)2H2O]2[MoV3MoVI5VIV8O40(PO4)]}·5H2O 3 , {[Co(2,2’-bipy)2H2O]4[MoV4MoVI4VIV8O40(PO4)]}{[Co(2,2’-bipy)2H2O]2[MoV3 MoVI5VIV8O40(PO4)]}(H3O)·4H2O 4, [Ni(phen)3]2H[PMoV4MoVI4 VIV6 M2O44]·4H2O 5 和[Co(phen)3]2H[PMoV4MoVI4 VIV6 M2O44]·4H2O 6. Their structure were determined by single crystal X-ray diffraction analysis and characterized by XPS, EPR, IR, ICP, TG, etc. The magnetic behavior of compound 1 、2、3 and 4 was measured, There exist antiferromagnetic interaction in 1, 3 and 4. There exists ferromagnetic interaction in 2. Compound 1 and 2 consist of highly reduced tetra or bi-capped pseudo-Keggin polyoxoanion supporting two transition complexes, modified polyoxometalates Compound 3, 4 are isostructural constructed of positive and negative metal-oxo cluster ions, Compound 5, 6 are isostuctural too, constructed of tetra-capped pseudo-Keggin polyoxoanion, but two V atoms on the V8 ring are replaced by Mo atoms. All the six compounds are in triclinic system with space group P-1, cell parameters: 1 a = 13.1098(2) ?, b = 14.2845(3) ?, c = 17.0576(4) ?, α= 90.7550(10)o, β= 104.6340(10)o, γ= 100.8690(10)o, V = 3029.03(11) ?3. 2 a = 14.5976(4) ?, b = 15.8988(4) ?, c = 16.2805(4) ?, α= 116.292(2)o, β= 102.968(2)o, γ= 94.841(2)o, V = 3227.29(14) ? 3. 3 a = 15.628(3) ?, b = 24.948(5) ?, c = 25.071(5) ?, α= 76.34(3) o, β= 78.11(3)o, γ= 80.39(3)o. 4 a = 15.722(3) ?, b = 25.000(5) ?, c = 25.315(5) ?, α= 76.40(3)o, β= 78.19(3)o, γ= 80.41(3)o, V = 9392(3) ?3. 5 a = 12.0953(7) ?, b = 14.0715(8) ?, c = 14.6211(8) ?, α= 105.1600(10)o, β= 92.1230(10)o, γ= 91.4210(10)o, V = 2398.7(2) ?3. 6 a = 12.1351(5) ?, b = 14.0182(6) ?, c = 14.6468(7) ?, α= 105.134(2)o, β= 91.841(3))o, γ= 91.401(2)o, V = 2402.55(18) ? 3.
2. Phosphorous -molybdate The hydrothermal reactions give a phosphorous-molybdate (NH3CH2CH2NH3) (NH3CH2CH2NH2)3Na3[Co4Moi2O24(OH)6(H2O)2(HPO4)2(PO4)6]-8H2O 7 and two cobalt molybdate NaCo2OH(H2O)(MoO4)2 8, NH4Mo6Oi8 9. The structure of compound 7 is based on Co[Mo6P4]2 units connected together via additional Co2+ ions to give a new three-dimensional framework. This is the first open-framework cobalt molybdenum phosphate constructed from M[Mo6P4]2 building blocks and containing both tetrahedrally and octahedrally coordinated transition metals. Compound 8 belongs to 3-D heavy-metal molybdate. Compound 9 is a polyoxomolybdate. Their structure were determined by single crystal X-ray diffraction analysis and characterized by IR, ICP. The magnetic behavior of compound 7 was measured; there exist antiferromagnetic interaction in 7. 7 crystallizes in monoclinic system with space group C2/c, cell parameters a = 12.328(3) A, b = 21.579(4) A, c = 26.024(5) A, 0 = 99.54(3)°, V = 6827(2) A3. 8 crystallizes in Monoclinic system with space group C2/m, cell parameters a = 9.3647(19)A, 6=6.3143(13), c = 7.6009(15) A, /3= 115.81(3)°, V = 404.62(14) A3. 9 crystallizes in Monoclinic system with space group P6(3)/m, cell parameters a = 10.6166(15) A, b = 10.6166(15), c = 3.7290(7), y = 120°, V = 363.99(10) A3. 3. Heteropoly and isopolyoxovanadate Hydrothermal reactions give four isovanadate [Co(2,2'-bipy)3]2[V4Oi2]-HH2O 10, [Co(2,2'-bipy)(H2O)(VO3)2] 11, [Co(l,10-phen)(H2O)(VO3)2] 12, [Cu(en)2]V6O14 13, and two heteropolyoxovanadate [Co(l,10-phen)3AsgVi4O42] 14, [Ni(l,10-phen)3 AS8V14O42] 15. Their structures were determined by single crystal X-ray diffraction analysis and characterized by IR, ICP, etc. 10 crystallizes in Monoclinic with space group C2/c, cell parameters a = 21.987(4) A, b = 14.025(3) A, c = 23.854(5) A, ]3 = 106.08(3)°, V = 7068(2) A3. 11 crystallizes in Orthorhombic with space group
Pca2(l), cell parameters a = 9.2280(2) A, b = 10.5604(3) A, c = 9.4684(19)A, V = 1401.51(7) A3, 12 crystallizes in Monoclinic with space group P2(l)/c, cell parameters a = 7.8623(16) A, b = 21.149(4) A, c = 23.854(5)A,^ = 112.87(3)°, V = 1450.7(5) A3. 13 crystallizes in Monoclinic with space group P2(l)/ n, cell parameters a = 8.9373(18)A, b =6.5175(13)A, c = 15.722(3) A, fi= 100.01(3)°, V = 901.8(3) A3. 4. Polyoxotungstate Three heteropoly tungstates [Co(2,2'-bipy)3]2{[Co(2,2'-bipy)]WV2Wvlio036 (CoO4)[Co(NH3)2]}-3H2O 16, [Ni(2,2'-bipy)3]2{[Ni(2,2'-bipy)]WV4WVI8O36(NiO4) [Ni(NH3)2]} 17 and [Co(l,10-phen)3]2{[Co(l,10-phen)]2WV2WVI10O36(CoO4)} 18 have been synthesized by using hydrothermal method. Their structures were determined by single crystal X-ray diffraction analysis and characterized by IR, ICP, etc. The feature of three compounds is that the Keggin unit capped by neighboring Co or Ni atom through bridging four u-2 oxygen atoms. 16 crystallizes in Monoclinic with space group P2(l)/n, cell parameters a = 18.776(4)A, b = 26.547(5) A, c = 19.782(4) A, 0 = 98.50(3)°, V = 9752(3) A3. 17 crystallizes in Monoclinic with space group P2(l)/n, cell parameters a = 18.8732(4)A, b = 26.6571(5) A, c = 19.7826(4) A, J3 = 98.252(3)°, V = 9849 A3. 18 crystallizes in Monoclinic with space group C2/c, cell parameters a = 27.3225(4)A, b = 14.6945(5) A, c = 25.9856(4) A, p = 97.987(3)°, V = 10331.8(3) A3. 5. Hetero-nuclear CuVCu11 compound involving hydroxylation of N-heterocycle ligands A novel compound [MoO3Cu2(obpy)2]2O 19 is the first hetero-nuclear molybdenum-copper cluster involving hydroxylation of N-heterocycle ligands, which has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR, XPS, ESR and elemental analysis. The magnetic behavior of
本文合成了六个混配型钼-钒-磷具有四帽或二帽的Keggin 结构的多金属氧酸盐。其中两个化合物是Keggin 结构的阴离子支撑两个过渡金属配合物,两个同构的阴、阳离子皆为支撑结构的多金属氧酸盐的化合物, 其中正离子是由混合钼-钒四帽Keggin 结构的簇阴离子支撑四个过渡金属配合物阳离子构成的,负离子是由混合钼-钒四帽Keggin 结构的阴离子支撑两个过渡金属配合物构成的(第三章)。合成了一个三维结构的钴钼磷酸盐和两个单钼的同多金属氧酸盐,在以[Mo_6P_4]为结构单元构筑的化合物中它是第一个同时包含四面体配位和八面体配位钴的钴钼磷酸盐(第四章)。四个单钒的同多金属氧酸盐,其中一个具有分立结构的钒酸盐带有十一个结晶水。这些水分子形成了规则的水簇,并通过氢键与簇阴离子[V_4O_(12)]_4-一起构成网络结构。两个钒-氧杂化材料是由钒氧簇和过渡金属配合物连接为二维的扩展结构,由邻菲啰啉间的π-π作用形成三维超分子结构。还有一个由无机钒氧层和有机过渡金属配合物组成的三维结构的化合物。两个砷-钒多金属氧酸盐(第五章)。三个具有镶嵌结构的钨氧簇合物,核心簇为Keggin 结构的[MW_(12)O_(40)]~(n-) (M = Co 或Ni)两边分别镶嵌一个Co(或Ni),这个镶嵌的Co(或Ni)分别与簇上的四个氧和两个其它的原子配位,其结构类型很新颖(第六章),以及一个涉及N 杂环配体原位羟化反应的异核的含混合价CuI/CuII 的化合物(第七章)。对本论文所合成的化合物进行X-射线衍射、红外、热重、顺磁及X-射线光电子能谱的结构表征。对部分化合物进行了磁学性能的测试和探讨。详细分析并阐述了上述化合物的合成条件和方法,温度、压力、浓度等对产物结构的影响,为该体系化合物的进一步研究奠定了基础。
Polyoxometalates (POMs) represent a fascinating class of inorganic chemistry with a structural variety and interesting properties, which are of use in fields as diverse as catalysis, sorption, molecular electronics, medicine, etc. A great progress in metal-oxo cluster chemistry has been study of polyoxoanion-supporting inorganic or organometallic complexes, in which Keggin unit and its derivative-supporting metal complexes is an important family. There exist two kinds of Keggin cluster-supported metal complexes. One is molecular clusters possessing discrete structures, the other is cluster polymers constructed from Keggin units as building blocks and metal complexes as bridges.
During our research for the metal-oxygen clusters, we synthesized some decorated metal-oxygen clusters, the cluster based on molybdenum-vanadium, cobalt phosphomolybdate, polyoxovanadate, polyoxotungstate and hetero-nuclear Cu'/Cu" compound involving hydroxylation of N-heterocycle ligands. On the bases of X-ray structural analyses, some compounds have been characterized by IR, XPS, ESR spectra. The thermal analyses and magnetic properties of some compounds have also been studied, which would take a role in the explorations of structures and functions for the compounds. 1. The mixed molybdenum-vanadium polyoxometalates.
The hydrothermal reactions give six novel compounds ,which consist of highly
reduced tetra or bi-capped pseudo-Keggin polyoxoanion supporting transition metal complexes, {[Co(phen)2]2-C2O4}{H2PMoVI3MoV5VIV8O44[Co(phen)2 (H2O)]2}·7H2O 1 和[Cu(phen)2]4{HPMo8VIVIV6O42[Cu(phen)]2}·2H2O 2,{[Ni(2,2’-bipy)2H2O]4 [MoV3MoVI5VIV8O40(PO4)]}{[Ni(2,2’-bipy)2H2O]2[MoV3MoVI5VIV8O40(PO4)]}·5H2O 3 , {[Co(2,2’-bipy)2H2O]4[MoV4MoVI4VIV8O40(PO4)]}{[Co(2,2’-bipy)2H2O]2[MoV3 MoVI5VIV8O40(PO4)]}(H3O)·4H2O 4, [Ni(phen)3]2H[PMoV4MoVI4 VIV6 M2O44]·4H2O 5 和[Co(phen)3]2H[PMoV4MoVI4 VIV6 M2O44]·4H2O 6. Their structure were determined by single crystal X-ray diffraction analysis and characterized by XPS, EPR, IR, ICP, TG, etc. The magnetic behavior of compound 1 、2、3 and 4 was measured, There exist antiferromagnetic interaction in 1, 3 and 4. There exists ferromagnetic interaction in 2. Compound 1 and 2 consist of highly reduced tetra or bi-capped pseudo-Keggin polyoxoanion supporting two transition complexes, modified polyoxometalates Compound 3, 4 are isostructural constructed of positive and negative metal-oxo cluster ions, Compound 5, 6 are isostuctural too, constructed of tetra-capped pseudo-Keggin polyoxoanion, but two V atoms on the V8 ring are replaced by Mo atoms. All the six compounds are in triclinic system with space group P-1, cell parameters: 1 a = 13.1098(2) ?, b = 14.2845(3) ?, c = 17.0576(4) ?, α= 90.7550(10)o, β= 104.6340(10)o, γ= 100.8690(10)o, V = 3029.03(11) ?3. 2 a = 14.5976(4) ?, b = 15.8988(4) ?, c = 16.2805(4) ?, α= 116.292(2)o, β= 102.968(2)o, γ= 94.841(2)o, V = 3227.29(14) ? 3. 3 a = 15.628(3) ?, b = 24.948(5) ?, c = 25.071(5) ?, α= 76.34(3) o, β= 78.11(3)o, γ= 80.39(3)o. 4 a = 15.722(3) ?, b = 25.000(5) ?, c = 25.315(5) ?, α= 76.40(3)o, β= 78.19(3)o, γ= 80.41(3)o, V = 9392(3) ?3. 5 a = 12.0953(7) ?, b = 14.0715(8) ?, c = 14.6211(8) ?, α= 105.1600(10)o, β= 92.1230(10)o, γ= 91.4210(10)o, V = 2398.7(2) ?3. 6 a = 12.1351(5) ?, b = 14.0182(6) ?, c = 14.6468(7) ?, α= 105.134(2)o, β= 91.841(3))o, γ= 91.401(2)o, V = 2402.55(18) ? 3.
2. Phosphorous -molybdate The hydrothermal reactions give a phosphorous-molybdate (NH3CH2CH2NH3) (NH3CH2CH2NH2)3Na3[Co4Moi2O24(OH)6(H2O)2(HPO4)2(PO4)6]-8H2O 7 and two cobalt molybdate NaCo2OH(H2O)(MoO4)2 8, NH4Mo6Oi8 9. The structure of compound 7 is based on Co[Mo6P4]2 units connected together via additional Co2+ ions to give a new three-dimensional framework. This is the first open-framework cobalt molybdenum phosphate constructed from M[Mo6P4]2 building blocks and containing both tetrahedrally and octahedrally coordinated transition metals. Compound 8 belongs to 3-D heavy-metal molybdate. Compound 9 is a polyoxomolybdate. Their structure were determined by single crystal X-ray diffraction analysis and characterized by IR, ICP. The magnetic behavior of compound 7 was measured; there exist antiferromagnetic interaction in 7. 7 crystallizes in monoclinic system with space group C2/c, cell parameters a = 12.328(3) A, b = 21.579(4) A, c = 26.024(5) A, 0 = 99.54(3)°, V = 6827(2) A3. 8 crystallizes in Monoclinic system with space group C2/m, cell parameters a = 9.3647(19)A, 6=6.3143(13), c = 7.6009(15) A, /3= 115.81(3)°, V = 404.62(14) A3. 9 crystallizes in Monoclinic system with space group P6(3)/m, cell parameters a = 10.6166(15) A, b = 10.6166(15), c = 3.7290(7), y = 120°, V = 363.99(10) A3. 3. Heteropoly and isopolyoxovanadate Hydrothermal reactions give four isovanadate [Co(2,2'-bipy)3]2[V4Oi2]-HH2O 10, [Co(2,2'-bipy)(H2O)(VO3)2] 11, [Co(l,10-phen)(H2O)(VO3)2] 12, [Cu(en)2]V6O14 13, and two heteropolyoxovanadate [Co(l,10-phen)3AsgVi4O42] 14, [Ni(l,10-phen)3 AS8V14O42] 15. Their structures were determined by single crystal X-ray diffraction analysis and characterized by IR, ICP, etc. 10 crystallizes in Monoclinic with space group C2/c, cell parameters a = 21.987(4) A, b = 14.025(3) A, c = 23.854(5) A, ]3 = 106.08(3)°, V = 7068(2) A3. 11 crystallizes in Orthorhombic with space group
Pca2(l), cell parameters a = 9.2280(2) A, b = 10.5604(3) A, c = 9.4684(19)A, V = 1401.51(7) A3, 12 crystallizes in Monoclinic with space group P2(l)/c, cell parameters a = 7.8623(16) A, b = 21.149(4) A, c = 23.854(5)A,^ = 112.87(3)°, V = 1450.7(5) A3. 13 crystallizes in Monoclinic with space group P2(l)/ n, cell parameters a = 8.9373(18)A, b =6.5175(13)A, c = 15.722(3) A, fi= 100.01(3)°, V = 901.8(3) A3. 4. Polyoxotungstate Three heteropoly tungstates [Co(2,2'-bipy)3]2{[Co(2,2'-bipy)]WV2Wvlio036 (CoO4)[Co(NH3)2]}-3H2O 16, [Ni(2,2'-bipy)3]2{[Ni(2,2'-bipy)]WV4WVI8O36(NiO4) [Ni(NH3)2]} 17 and [Co(l,10-phen)3]2{[Co(l,10-phen)]2WV2WVI10O36(CoO4)} 18 have been synthesized by using hydrothermal method. Their structures were determined by single crystal X-ray diffraction analysis and characterized by IR, ICP, etc. The feature of three compounds is that the Keggin unit capped by neighboring Co or Ni atom through bridging four u-2 oxygen atoms. 16 crystallizes in Monoclinic with space group P2(l)/n, cell parameters a = 18.776(4)A, b = 26.547(5) A, c = 19.782(4) A, 0 = 98.50(3)°, V = 9752(3) A3. 17 crystallizes in Monoclinic with space group P2(l)/n, cell parameters a = 18.8732(4)A, b = 26.6571(5) A, c = 19.7826(4) A, J3 = 98.252(3)°, V = 9849 A3. 18 crystallizes in Monoclinic with space group C2/c, cell parameters a = 27.3225(4)A, b = 14.6945(5) A, c = 25.9856(4) A, p = 97.987(3)°, V = 10331.8(3) A3. 5. Hetero-nuclear CuVCu11 compound involving hydroxylation of N-heterocycle ligands A novel compound [MoO3Cu2(obpy)2]2O 19 is the first hetero-nuclear molybdenum-copper cluster involving hydroxylation of N-heterocycle ligands, which has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR, XPS, ESR and elemental analysis. The magnetic behavior of
引文
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