稀土金属配合物的合成、结构及磁性研究
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摘要
近年来，利用稀土金属离子尤其是Dy~(3+), Tb~(3+), Ho~(3+), Er~(3+)和Yb~(3+)构筑单分子磁体（SMMs），提高自旋翻转能垒的研究，受到了人们的极大关注。其中最关键的要素之一就是选择、设计具有不同结构特点和配位能力的配体。本论文选用邻香兰素缩邻氨基苯甲酸席夫碱作为配体(H_2L)。由于该配体包含4个不同类型的配位氧原子和1个氮原子，对金属离子可表现出不同的配位能力，使其具有丰富的配位模式。同时，改变反应条件，可使配体发生一定程度的分解，形成H_2L、邻氨基苯甲酸和邻香兰素三种配体混合共存的体系，有望得到具有新颖结构和良好性能的配合物。基于此，本论文中我们通过改变桥联配体、反应条件、复合高自旋基态过渡金属离子等方法，组装合成了结构新颖的3个系列的同多核稀土金属配合物（配合物1-13）,1个系列的4f或3d-4f一维链状配合物（配合物14-18）和2个系列的低核数稀土金属配合物（配合物19-25），并详细研究了这些化合物的结构和磁性质。结果表明，有3个化合物表现出了单分子磁体慢弛豫行为，1个化合物表现出了单链磁体行为。结果简述如下：
1.通过溶剂热的制备方法，合成出基于硝酸根桥联的四个同构八核稀土簇合物[Na_2Ln_6L_8(C_6H_4NH_2COO)_2(C_2H_5OH)_2(H_2O)_4(NO_3)]·NO_3·C_2H_5OH·nH_2O [Ln=Dy(1)(n=15); Tb (2), Gd (3)(n=14); Sm (4)(n=16)]。结构分析表明，在配合物中一个硝酸根离子通过μ8-η2:η2:η4三齿配位模式连接了八个金属离子，其中六个稀土离子以[4+2]连接模式构建出一种新颖的Ln6拓扑构型，不同于以往报道的由Ln3三角以“边到边”或“头到头”形成的Ln6结构。磁性测试结果表明，配合物1表现出频率相关的交流虚部信号，表现出单分子磁体磁化强度慢弛豫现象。
2.通过增加反应体系碱性，构建了3个基于μ3-OH桥联的高核数同多核稀土金属配合物[Dy_8L_4L'_2L''_2(μ3-OH)_6(NO_3)_6]·8(H_2O)(5)，[Ln_(10)L_6L'_2L''_2(μ3-OH)_6(μ2-OH)_2(H_2O)_2(NO_3)_4]·2(NO_3)·8(H_2O)·(C_2H_5OH)(Ln=Er (6);Ho(7))。结构分析表明，3个化合物中均包含4个经典的单、双盖帽Ln3三角单元，其中每两个Ln3三角单元之间以共边形式连接，再通过不同数目羧酸根桥联，形成了中心对称的立方体(5)或双帽四棱柱构型(6,7)核结构。磁性测试分析表明，簇合物5表现磁化强度慢弛豫行为。
3.首次利用硅酸根离子SiO_4~(4-)作为辅助桥联配体，通过其特殊的μ8:η~3:η~3:η~3:η~3配位模式，将8个稀土金属离子连接在一起，形成了具有笼状三层结构的化合物[Ln_8L_8(C_6H_4NH_2COO)_4SiO_4](Ln=Dy(8), Tb(9), Gd(10), Nd(11), Pr(12), Sm(13))。结构分析表明，配合物中8个Ln~(3+)平行分布于三个平面中，稀土离子之间的距离较小，存在不可忽略的磁相互作用。磁性测试结果表明，配合物8具有强的磁各向异性，表现出频率相关的单分子磁体行为。这是第一例利用硅酸根构筑的稀土金属配合物。
4.通过复合过渡金属元素Co, Ni或者与纯稀土离子反应，得到了2种3d-4f一维链化合物{[Dy_2M_2L_4(NO_3)(H_2O)_2][Dy_2M_2L_4(NO_3)(CH_3COO)(H_2O)]·(NO_3)}n(M=Co(14), Ni(15))，2个纯稀土离子构成的一维梯子链[LnL'(C_2H_5OH)(NO_3)_2]n(Ln=Pr(16), Nd(17))和1个稀土离子一维链[PrL'3]n(18)。结构分析表明，配合物14和15具有类似DNA构型的双一维梯子链结构。而配合物16-18中，稀土离子间完全通过硝酸根或者3个羧基氧原子桥联，说明离子间存在比较有效的相互作用。磁性测试表明，配合物15表现出交流磁化率虚部的频率依赖，可能具有单链磁体的性质。
5.通过调控反应体系碱性，制备出了2个同构的六核配合物[Ln_6L_6(μ4-H_2O)(NO_3)_6(H_2O)_2]·C_2H_5OH(Ln=Pr(19), Nd(20))和5个同构的双核配合物[Ln_2(HL)_2(NO_3)_4(C_2H_5OH)_2(H_2O)_2](Ln=Tb(21), Eu(22),Gd(23), Er(24), Nd(25))。结构分析表明，化合物19，20为具有新颖[4+2]构型的六核化合物，其中立方烷Ln4中心存在一个μ4-O氧原子，同四个金属中心的距离都为2.36，所形成的6个夹角∠Ln-O-Ln均大于100，表明金属离子间可能具有较好的相互作用。而双核配合物分子呈中心对称，可能导致金属离子低的磁轴向性，不利于材料磁性质的表现。磁性质测试表明，配合物21中离子间具有弱铁磁性相互作用，但是没有交流虚部信号，不具有单分子磁体的性质。
Recently, studies on the synthesis of polynuclear lanthanide-based single-moleculemagnets have received considerable attention, especially for the Dy~(3+), Tb~(3+), Ho~(3+), Er~(3+)and Yb~(3+)ions. To obtain lanthanide clusters with novel topologies, the selection ofligand and bridging ligand is one of the key factors. In this thesis, the polydentate Schiffbase2-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzoic acid (H_2L) hasbeen used as the ligand, because it has four different kinds of oxygen atoms and onenitrogen atom, and shows various coordination modes. Meanwhile, by changing thereaction conditions, the ligand may be decomposed to the two reactants, anthranilic acidand o-vanillin. Therefore the coexistence of three ligands may lead to a great number ofcomplexes with novel topologies and superior properties.
Based on the considerations mentioned above, we have prepared three types ofhigher-nuclearity homometallic lanthanoid clusters (1-13), one type of3d-4f/4f singlechain complexes (14-18) and two types of lower-nuclearity lanthanide clusters (19-25)by alternating the bridging ligands, pH values of the reaction system or combining withthe3d transition metals. The crystal structures and magnetic properties of them havebeen studied. The results showed that among of them, three complexes showfield-induced slow relaxation of magnetization while1complex may show single chainmagnet properties. The results of this thesis are briefly summarized as follows.
1. A family of new octanuclear lanthanide compounds[Na_2Ln_6L_8(C_6H_4NH_2COO)_2(C_2H_5OH)_2(H_2O)_4(NO_3)]·NO_3·C_2H_5OH·nH_2O [H_2L=2-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzoic acid; Ln=Dy (1)(n=15); Tb (2), Gd (3)(n=14); Sm (4)(n=16)] have been prepared under hydrothermalconditions. The X-ray crystal structure analysis reveals that a nitrate ion, which displaysan unusual μ8-η2:η2:η4tridentate bridging mode and bridges all the eight metal ions, islocated in the center of the cluster. The core of the structure is a [4+2] combination of anLn4cubane and an Ln_2unit, which is quite different from previously reported Ln6cases. Alternating current susceptibility measurements reveal that the DyIII–containing cluster[Na2Dy6] exhibits slow relaxation of magnetization.
2. By increasing the pH value of the reaction system, three higher nuclearityhomometallic lanthanoid clusters,[Dy_8L_4L'_2L''_2(μ3-OH)_6(NO_3)_6]·8(H_2O)(5)，[Ln_(10)L_6L'_2L''_2(μ3-OH)_6(μ2-OH)_2(H_2O)_2(NO_3)_4]·2(NO_3)·8(H_2O)·(C_2H_5OH)(Ln=Er (6);Ho(7)), have been successfully obtained. The crystal structures and magnetic propertiesof them have been studied. All the3complexes have four typical mono-, bi-cappedtriangles and then was linked to each other by carboxylate oxygen atoms, leading tosystematic cubic (5) or bi-capped (6,7) square prism core geometry. Alternating currentsusceptibility measurements revealed that the DyIII–containing cluster [Dy8] exhibitsslow relaxation of magnetization.
3. The first examples of silicate bridging lanthanide clusters,[Ln_8L_8(C_6H_4NH_2COO)_4SiO_4] Ln=Dy(8), Tb(9), Gd(10), Nd(11), Pr(12), Sm(13)] havebeen obtained via hydrothermal reaction by using sodium silicate as bridging ligand.Crystal structural analysis shows that one silicate ion located in the center of the clusteradopts a μ8:η~3:η~3:η~3:η~3tetradentate bridging mode, and this [SiO_4] core binds to all theLn(III) ions generating the [Ln8SiO_4] cluster. Within the cluster eight Ln(III) ions arearranged in an unprecedented three-layer structure. The short Ln…Ln distance revealsunnegligible magnetic interaction between them. Magnetic studies indicate that the[Dy8SiO_4] complex exhibits slow relaxation of magnetization. The [Ln8SiO_4] complexrepresents the first lanthanide cluster based on the silicate building block.
4. Five single chain complexes with three types of structures, namely, twoisostructural3d4f heterometallic single chaincomplexes{[Dy_2M_2L_4(NO_3)(H_2O)_2][Dy_2M_2L_4(NO_3)(CH_3COO)(H_2O)]·(NO_3)}n(M=Co(14), Ni(15))，two pure4f single chain complexes [LnL'(C_2H_5OH)(NO_3)_2]n(Ln=Pr(16), Nd(17)) and one4f single chain complex [PrL'3]n, have been reported. Crystalstructural analysis showed that the3d4f heterometallic complexes have an interestingbi-ladder single chain structures similar to the DNA molecule structure, while thecomplexes16and17have the ladder single chain structures and18only shows singlechain motif. Furthermore, the metal ions in complexes16-18were connected via nitrateions or three O atoms from the carboxylate groups, indicating strong interactionsbetween them. Alternating current susceptibility measurements reveal that the DyIII-NiII containing complex shows a strong frequency dependency, thus may exhibit slowrelaxation of magnetization as a SCM.
5. Two hexanuclear complexes [Ln_6L_6(μ4-H_2O)(NO_3)_6(H_2O)_2]·C_2H_5OH(Ln=Pr(19), Nd(20)) and five isomorphic dinuclear complexes[Ln_2(HL)_2(NO_3)_4(C_2H_5OH)_2(H_2O)_2](Ln=Tb(21), Eu(22),Gd(23), Er(24), Nd(25)) havebeen prepared with or without the addition of NaOH to the reaction system. Resultsshowed that complexes19-20have new type of [4+2] topology, in which the Ln4unitshows a typical cubane motif with a μ4-H_2O being located in its center. The distance ofμ4-O…Ln~(3+)is2.36and the angles of Ln-μ4-O-Ln are in the range of100.2-114.2,indicating efficient interactions between the metal ions. The dinuclear complexes arecentrosymmetric which may lead to the low magnetic axiality and thus being not goodfor magnetic property. Magnetic studies indicate the [Tb2] complex exhibitsferromagnetic interactions without an out-of-phase signal.
1.通过溶剂热的制备方法，合成出基于硝酸根桥联的四个同构八核稀土簇合物[Na_2Ln_6L_8(C_6H_4NH_2COO)_2(C_2H_5OH)_2(H_2O)_4(NO_3)]·NO_3·C_2H_5OH·nH_2O [Ln=Dy(1)(n=15); Tb (2), Gd (3)(n=14); Sm (4)(n=16)]。结构分析表明，在配合物中一个硝酸根离子通过μ8-η2:η2:η4三齿配位模式连接了八个金属离子，其中六个稀土离子以[4+2]连接模式构建出一种新颖的Ln6拓扑构型，不同于以往报道的由Ln3三角以“边到边”或“头到头”形成的Ln6结构。磁性测试结果表明，配合物1表现出频率相关的交流虚部信号，表现出单分子磁体磁化强度慢弛豫现象。
2.通过增加反应体系碱性，构建了3个基于μ3-OH桥联的高核数同多核稀土金属配合物[Dy_8L_4L'_2L''_2(μ3-OH)_6(NO_3)_6]·8(H_2O)(5)，[Ln_(10)L_6L'_2L''_2(μ3-OH)_6(μ2-OH)_2(H_2O)_2(NO_3)_4]·2(NO_3)·8(H_2O)·(C_2H_5OH)(Ln=Er (6);Ho(7))。结构分析表明，3个化合物中均包含4个经典的单、双盖帽Ln3三角单元，其中每两个Ln3三角单元之间以共边形式连接，再通过不同数目羧酸根桥联，形成了中心对称的立方体(5)或双帽四棱柱构型(6,7)核结构。磁性测试分析表明，簇合物5表现磁化强度慢弛豫行为。
3.首次利用硅酸根离子SiO_4~(4-)作为辅助桥联配体，通过其特殊的μ8:η~3:η~3:η~3:η~3配位模式，将8个稀土金属离子连接在一起，形成了具有笼状三层结构的化合物[Ln_8L_8(C_6H_4NH_2COO)_4SiO_4](Ln=Dy(8), Tb(9), Gd(10), Nd(11), Pr(12), Sm(13))。结构分析表明，配合物中8个Ln~(3+)平行分布于三个平面中，稀土离子之间的距离较小，存在不可忽略的磁相互作用。磁性测试结果表明，配合物8具有强的磁各向异性，表现出频率相关的单分子磁体行为。这是第一例利用硅酸根构筑的稀土金属配合物。
4.通过复合过渡金属元素Co, Ni或者与纯稀土离子反应，得到了2种3d-4f一维链化合物{[Dy_2M_2L_4(NO_3)(H_2O)_2][Dy_2M_2L_4(NO_3)(CH_3COO)(H_2O)]·(NO_3)}n(M=Co(14), Ni(15))，2个纯稀土离子构成的一维梯子链[LnL'(C_2H_5OH)(NO_3)_2]n(Ln=Pr(16), Nd(17))和1个稀土离子一维链[PrL'3]n(18)。结构分析表明，配合物14和15具有类似DNA构型的双一维梯子链结构。而配合物16-18中，稀土离子间完全通过硝酸根或者3个羧基氧原子桥联，说明离子间存在比较有效的相互作用。磁性测试表明，配合物15表现出交流磁化率虚部的频率依赖，可能具有单链磁体的性质。
5.通过调控反应体系碱性，制备出了2个同构的六核配合物[Ln_6L_6(μ4-H_2O)(NO_3)_6(H_2O)_2]·C_2H_5OH(Ln=Pr(19), Nd(20))和5个同构的双核配合物[Ln_2(HL)_2(NO_3)_4(C_2H_5OH)_2(H_2O)_2](Ln=Tb(21), Eu(22),Gd(23), Er(24), Nd(25))。结构分析表明，化合物19，20为具有新颖[4+2]构型的六核化合物，其中立方烷Ln4中心存在一个μ4-O氧原子，同四个金属中心的距离都为2.36，所形成的6个夹角∠Ln-O-Ln均大于100，表明金属离子间可能具有较好的相互作用。而双核配合物分子呈中心对称，可能导致金属离子低的磁轴向性，不利于材料磁性质的表现。磁性质测试表明，配合物21中离子间具有弱铁磁性相互作用，但是没有交流虚部信号，不具有单分子磁体的性质。
Recently, studies on the synthesis of polynuclear lanthanide-based single-moleculemagnets have received considerable attention, especially for the Dy~(3+), Tb~(3+), Ho~(3+), Er~(3+)and Yb~(3+)ions. To obtain lanthanide clusters with novel topologies, the selection ofligand and bridging ligand is one of the key factors. In this thesis, the polydentate Schiffbase2-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzoic acid (H_2L) hasbeen used as the ligand, because it has four different kinds of oxygen atoms and onenitrogen atom, and shows various coordination modes. Meanwhile, by changing thereaction conditions, the ligand may be decomposed to the two reactants, anthranilic acidand o-vanillin. Therefore the coexistence of three ligands may lead to a great number ofcomplexes with novel topologies and superior properties.
Based on the considerations mentioned above, we have prepared three types ofhigher-nuclearity homometallic lanthanoid clusters (1-13), one type of3d-4f/4f singlechain complexes (14-18) and two types of lower-nuclearity lanthanide clusters (19-25)by alternating the bridging ligands, pH values of the reaction system or combining withthe3d transition metals. The crystal structures and magnetic properties of them havebeen studied. The results showed that among of them, three complexes showfield-induced slow relaxation of magnetization while1complex may show single chainmagnet properties. The results of this thesis are briefly summarized as follows.
1. A family of new octanuclear lanthanide compounds[Na_2Ln_6L_8(C_6H_4NH_2COO)_2(C_2H_5OH)_2(H_2O)_4(NO_3)]·NO_3·C_2H_5OH·nH_2O [H_2L=2-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzoic acid; Ln=Dy (1)(n=15); Tb (2), Gd (3)(n=14); Sm (4)(n=16)] have been prepared under hydrothermalconditions. The X-ray crystal structure analysis reveals that a nitrate ion, which displaysan unusual μ8-η2:η2:η4tridentate bridging mode and bridges all the eight metal ions, islocated in the center of the cluster. The core of the structure is a [4+2] combination of anLn4cubane and an Ln_2unit, which is quite different from previously reported Ln6cases. Alternating current susceptibility measurements reveal that the DyIII–containing cluster[Na2Dy6] exhibits slow relaxation of magnetization.
2. By increasing the pH value of the reaction system, three higher nuclearityhomometallic lanthanoid clusters,[Dy_8L_4L'_2L''_2(μ3-OH)_6(NO_3)_6]·8(H_2O)(5)，[Ln_(10)L_6L'_2L''_2(μ3-OH)_6(μ2-OH)_2(H_2O)_2(NO_3)_4]·2(NO_3)·8(H_2O)·(C_2H_5OH)(Ln=Er (6);Ho(7)), have been successfully obtained. The crystal structures and magnetic propertiesof them have been studied. All the3complexes have four typical mono-, bi-cappedtriangles and then was linked to each other by carboxylate oxygen atoms, leading tosystematic cubic (5) or bi-capped (6,7) square prism core geometry. Alternating currentsusceptibility measurements revealed that the DyIII–containing cluster [Dy8] exhibitsslow relaxation of magnetization.
3. The first examples of silicate bridging lanthanide clusters,[Ln_8L_8(C_6H_4NH_2COO)_4SiO_4] Ln=Dy(8), Tb(9), Gd(10), Nd(11), Pr(12), Sm(13)] havebeen obtained via hydrothermal reaction by using sodium silicate as bridging ligand.Crystal structural analysis shows that one silicate ion located in the center of the clusteradopts a μ8:η~3:η~3:η~3:η~3tetradentate bridging mode, and this [SiO_4] core binds to all theLn(III) ions generating the [Ln8SiO_4] cluster. Within the cluster eight Ln(III) ions arearranged in an unprecedented three-layer structure. The short Ln…Ln distance revealsunnegligible magnetic interaction between them. Magnetic studies indicate that the[Dy8SiO_4] complex exhibits slow relaxation of magnetization. The [Ln8SiO_4] complexrepresents the first lanthanide cluster based on the silicate building block.
4. Five single chain complexes with three types of structures, namely, twoisostructural3d4f heterometallic single chaincomplexes{[Dy_2M_2L_4(NO_3)(H_2O)_2][Dy_2M_2L_4(NO_3)(CH_3COO)(H_2O)]·(NO_3)}n(M=Co(14), Ni(15))，two pure4f single chain complexes [LnL'(C_2H_5OH)(NO_3)_2]n(Ln=Pr(16), Nd(17)) and one4f single chain complex [PrL'3]n, have been reported. Crystalstructural analysis showed that the3d4f heterometallic complexes have an interestingbi-ladder single chain structures similar to the DNA molecule structure, while thecomplexes16and17have the ladder single chain structures and18only shows singlechain motif. Furthermore, the metal ions in complexes16-18were connected via nitrateions or three O atoms from the carboxylate groups, indicating strong interactionsbetween them. Alternating current susceptibility measurements reveal that the DyIII-NiII containing complex shows a strong frequency dependency, thus may exhibit slowrelaxation of magnetization as a SCM.
5. Two hexanuclear complexes [Ln_6L_6(μ4-H_2O)(NO_3)_6(H_2O)_2]·C_2H_5OH(Ln=Pr(19), Nd(20)) and five isomorphic dinuclear complexes[Ln_2(HL)_2(NO_3)_4(C_2H_5OH)_2(H_2O)_2](Ln=Tb(21), Eu(22),Gd(23), Er(24), Nd(25)) havebeen prepared with or without the addition of NaOH to the reaction system. Resultsshowed that complexes19-20have new type of [4+2] topology, in which the Ln4unitshows a typical cubane motif with a μ4-H_2O being located in its center. The distance ofμ4-O…Ln~(3+)is2.36and the angles of Ln-μ4-O-Ln are in the range of100.2-114.2,indicating efficient interactions between the metal ions. The dinuclear complexes arecentrosymmetric which may lead to the low magnetic axiality and thus being not goodfor magnetic property. Magnetic studies indicate the [Tb2] complex exhibitsferromagnetic interactions without an out-of-phase signal.
引文
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