手性金属簇合物因结合了手性化合物和金属簇合物各自已有的性质，有可能同时呈现出光、电、磁、热和催化当中的两种及其以上的性质，是一类潜在的多功能材料。因此，合理地设计与合成这类具有多功能性质的化合物具有十分重要的意义。然而，目前文献中报道的手性金属簇合物并不多，其性质和应用还有待丰富和拓展。在此背景下，我们进行了以手性金属簇合物的合成、结构与性质研究为题的论文工作。在本论文中，我们探索了3d、3d-4f和4d-4f三个系列的手性金属簇合物的合成与组装规律，解析了它们的单晶结构并主要研究了它们的磁学性质。主要内容如下： 一、手性3d金属簇合物。以单一手性希夫碱H3L1为桥连配体，合成了具有C3...Chiral polymetallic clusters are potential multifunctional materials that display optical, electrical, magnetic, thermal and catalytic properties and/or other synergetic effects, due to the integration of chirality and special properties of metal clusters. Thus, rational design and synthesis of chiral polymetallic clusters are of key importance for the application of the materials. However, not on...学位：理学博士院系专业：化学化工学院化学系_无机化学学号：2052009015331

郑勇

Xiamen University Institutional Repository

厦门大学博硕士论文摘要库    Synthesis，Structures and Properties of Chiral Polymetallic Clusters   A Dissertation Submitted to the Graduate School in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy  By Yong Zheng  Supervised by Prof. La-Sheng Long    Department of Chemistry Xiamen University June, 2012  厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库 vi 厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库目 录 i 目  录 中文摘要 ................................................................................................................... I 英文摘要 ................................................................................................................ III 本论文所用的有机配体及缩写 ..............................................................................V 测试方法和仪器 .................................................................................................... VI 第一章 绪 论 .......................................................................................................1 1.1 引言..................................................................................................................1 1.2 手性金属簇合物的涵义 .................................................................................2 1.3 手性金属簇合物的研究意义和研究现状 .....................................................2 1.3.1 手性过渡(3d)金属簇合物.................................................................4 1.3.2 手性稀土-过渡(3d-4f)金属簇合物...................................................9 1.3.3 手性稀土(4f)金属簇合物 ................................................................ 11 1.4 本论文的选题背景与研究内容 ...................................................................13 参考文献: .............................................................................................................14 第二章 手性 3d 金属簇合物的合成、结构及性质 ...............................23 2.1 手性 Mn3 簇的单晶到单晶结构转变研究 ..................................................24 2.2 手性 Mn12 簇的合成、结构及磁性 .............................................................30 本章小结 ..............................................................................................................35 参考文献: .............................................................................................................36 第三章 手性 3d-4f 金属簇合物的合成、结构及性质..........................43 3.1 手性 Ln3Mn6 簇的合成、结构及磁性 ........................................................44 3.2 手性 Ln3Mn6 簇分步自组装构筑手性配位聚合物 ....................................54 本章小结 ..............................................................................................................65 参考文献 ..............................................................................................................66 第四章 手性 4d-4f 金属簇合物的合成、结构及性质..........................85 4.1 S4 对称性 Ln6Mo4 簇合物晶体的对称性调控 .............................................86 4.2 手性 Ln12Mo4 簇的合成、结构及磁热性质 .............................................104 本章小结 ............................................................................................................ 111 参考文献: ........................................................................................................... 112 第五章 总结和展望........................................................................................137 在学期间发表的论文 ...........................................................................................139 致 谢 .....................................................................................................................141 厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库Table of Contents iii Table of Contents Abstract in Chinese…………………………………………………….………..I Abstract in English……………………………………………………………III Organic Ligands and Abbreviations Used in This Paper……… …… V Measurements and Instruments ………………………………… VI Chapter I Introduction………………………………………………….……….1 1.1 Preface………. ………. ………. ………. ………. ……….…….…..………1 1.2 The chirality of polymetallic clusters...…………………………………….2 1.3 Introduction of researches about chiral polymetallic clusters…….………2   1.3.1 Chiral 3d polymetallic clusters…………………………………………4   1.3.2 Chiral 3d-4f polymetallic clusters………………………………………9   1.3.3 Chiral 4f polymetallic clusters…………………………………………11 1.4 The background and research contents. …………………….…………...…13 References……………………….…………….…………….………...…….……14 Chapter II Synthesis, Structures and Properties of Chiral 3d Clusters……….……….. ……….……….. ……….……….. ..23 2.1 Single-crystal-to-single-crystal transformation of a chiral Mn3 cluster…24 2.2 Synthesis, structure and magnetic properties of a chiral Mn12 cluster….30 Conclusion………………………………………………………………………...35 References……………………….…………………………….…………….……36 Chapter III Synthesis, Structures and Properties of Chiral 3d-4f Clusters……………………………………………………..……43 3.1 Synthesis, structures and magnetic properties of Ln3Mn6 clusters………44 3.2 Stepwise assembly of chiral coordination polymers from Ln3Mn6 clusters……………………………………………………………………54 Conclusion…………………………………………………………………...……65 References………………………………………………………………………....66 Chapter IV Synthesis, Structures and Properties of Chiral 4d-4f Clusters………………………………………………………….85   4.1 Manipulation over the symmetry of crystals consisting of S4 symmetric Ln6Mo4 clusters…. ………………………. ……. ……. ……. ……. …. ……. ...86   4.2 Synthesis, structures and magnetocaloric effect of Ln12Mo4 clusters…104 厦门大学博硕士论文摘要库厦门大学理学博士学位论文 iv Conclusion…………………………………………………………………..…111 References…………………………………………………………………...….112 Chapter V Summary and Outlook………………………………..……137 Appendix……….………….…………………………………………...…………139 Acknowledgments…..……………………………………………...…………141  厦门大学博硕士论文摘要库摘 要 I 摘 要 手性金属簇合物因结合了手性化合物和金属簇合物各自已有的性质，有可能同时呈现出光、电、磁、热和催化当中的两种及其以上的性质，是一类潜在的多功能材料。因此, 合理地设计与合成这类具有多功能性质的化合物具有十分重要的意义。然而, 目前文献中报道的手性金属簇合物并不多，其性质和应用还有待丰富和拓展。在此背景下，我们进行了以手性金属簇合物的合成、结构与性质研究为题的论文工作。在本论文中，我们探索了 3d、3d-4f 和 4d-4f 三个系列的手性金属簇合物的合成与组装规律，解析了它们的单晶结构并主要研究了它们的磁学性质。主要内容如下：  一、手性 3d 金属簇合物。以单一手性希夫碱 H3L1 为桥连配体，合成了具有C3 对称性的手性金属簇合物 Mn3 (1)，并且通过单晶-单晶结构转变的方式得到了类似结构的手性金属簇合物 Mn3 (2)。同时，利用单一手性希夫碱配体 H3L2 和非手性的第二配体(Hdhap)，得到了具有 D3 对称性的手性金属簇合物 Mn12 (3)。磁性研究表明，化合物 2 具有铁磁耦合作用，没有明显的磁各向异性；而化合物 3整体上表现出反铁磁耦合作用，并表现出磁各向异性。  二、手性 3d-4f 金属簇合物。首先，根据“金属配体法”策略，利用单一手性希夫碱配体 H3L1 桥连 LnIII 离子和 MnIII 离子，得到了同构的手性金属簇合物Ln3Mn6 (4-8)。CD 光谱及质谱研究表明，这些手性 Ln3Mn6 簇合物在碱性溶液中具有良好的稳定性。然后，采用分步自组装的办法，分别用异烟酸配体和甲酸钠将簇合物 4、5 和 8 连接成了具有 Kagome 拓扑结构的 2D 手性配位聚合物(9-11)以及具有 srs-SiO2 拓扑结构的 3D 手性配位聚合物(12-14)，实现了以手性 3d-4f金属簇合物为节点的配位聚合物的分步自组装。  三、手性 4d-4f 金属簇合物。利用 4d 金属酸根阴离子能同时与金属离子和有机配体(rac-H3L3)配位的特点，将其引入到高核稀土金属簇合物的合成中，得到厦门大学博硕士论文摘要库厦门大学理学博士学位论文 II 了两类结构新颖的4d-4f金属簇合物：S4对称性的Ln6Mo4和C3对称性的Ln12Mo4。结构分析表明，通过改变有机胺阳离子的大小，可使非手性的 Ln6Mo4阴离子簇结晶为中心晶体(15-17)，也可使之以外消旋聚集体形式结晶为手性晶体(18、19和 20、21)。手性金属簇合物 Ln12Mo4(22-24)结晶为中心晶体，具有截角四面体的骨架结构。在这类结构中，单个的 MoO42-离子不仅可以作为配体用氧原子桥连 LnIII离子，而且能够作为金属中心以 Mo 原子和有机配体配位，是一个双功能结构单元。这一发现既丰富了 Mo 元素的配位化学，又为合成高核稀土金属簇合物提供了新的思路。值得一提的是，化合物 15 和 18 表现出单分子磁体行为；而化合物 17、19 和 22 则具有较大磁熵变化。   关键词：手性金属簇合物；金属簇合物；手性；结构调控；磁性  厦门大学博硕士论文摘要库Abstract III Abstract Chiral polymetallic clusters are potential multifunctional materials that display optical, electrical, magnetic, thermal and catalytic properties and/or other synergetic effects, due to the integration of chirality and special properties of metal clusters. Thus, rational design and synthesis of chiral polymetallic clusters are of key importance for the application of the materials. However, not only a few of chiral polymetallic clusters have been explored so far, but also rational design and synthesis of chiral polymetallic clusters remain a great challenge. Accordingly, we focus our research on the rational design and synthesis of chiral polymetallic clusters and investigation on the magnetic properties of these clusters, resulting in three types of chiral polynuclear cluster, viz. 3d, 3d-4f and 4d-4f metal clusters, as follows: Firstly, a chiral C3-symmetric cluster of Mn3 (1) was synthesized based on the enantiopure Schiff-base ligand (H3L1, (S,E)-4-(2-hydroxybenzylideneamino)-2- hydroxybutanoic acid). And a similar chiral cluster of Mn3 (2) was generated through a single-crystal-to-single-crystal (SCSC) transformation from Mn3 (1). By the combination of an enantiopure Schiff-base ligand (H3L2, (S,E)-4-(1-(3,5-dichloro-2-hydroxyphenyl)ethylideneamino)-2-hydroxybutanoic acid) and achiral co-ligand (Hdhap, 1-(3,5-dichloro-2-hydroxyphenyl)ethanone), a chiral cluster Mn12 (3) in D3 symmetry was obtained. While 2 behaves ferromagnetic property without anisotropic, 3 shows antiferromagnetic behavior with obvious magnetic anisotropy. Secondly, based on the concept of metalloligand, five isostructural enantiopure sandwich-type LnIII3MnIII6 clusters (4-8) were synthesized with enantiopure Schiff-base ligand H3L1. Both circular dichroism (CD) spectra and electrospray ionization mass spectrometry (ESI-MS) demonstrated the high stability of 4-8 in basic organic solution. By utilizing isonicotinate and sodium formate as linkers, three two-dimensional homochiral coordination polymers (9-11) with Kagome topology and three three-dimensional homochiral coordination polymers (12-14) with srs-SiO2 topology were constructed in a stepwise assembly fashion from clusters 4, 5 and 8, respectively. Preliminary magnetic test indicates that the magnetic nature of the precursor was transformed into the final coordination polymers.  厦门大学博硕士论文摘要库厦门大学理学博士学位论文 IV Finally, by taking the advantage of oxometalates, which can not only act as a ligand to coordinate to the metal centers, but also function as a metal centre to be coordinated by organic ligands, Two types of unprecedented 4d-4f clusters, viz. Ln6Mo4 and Ln12Mo4, were synthesized by the corporation of oxomolybdate and racemic Schiff-base ligand (H3L3, (E)-2-((2,3-dihydroxypropylimino)methyl)phenol). The S4-symmetric anionic clusters of Ln6Mo4 can crystallize into both centrosymmetric crystal (15-17) and chiral crystals as conglomerate (18-19 and 20-21), only depending on the size of counter cations. This observation shows a special approach to chiral compounds from achiral resources. The C3-symmetric clusters of Ln12Mo4 (22-24) feature a truncated tetrahedron core {Ln12} capped by four MoO42- anions. And it was firstly found that discrete tetrahedral MoO42- anions can directly coordinate by organic ligands, and act as both a ligand and a metal centre in the formation of metal clusters. More significantly, while 15 and 18 are potential single-molecule magnet, 17, 19 and 22 exhibit a large magnetocaloric effect. This work not only helps us to understand the coordination chemistry of the MoO42- anion, but also provides new insights into the synthesis of high-nuclearity lanthanide-transition metal clusters with enhanced magnetic properties.  Keywords: cluster; chirality; polynuclear coordination complexes; structural manipulation; magnetism   厦门大学博硕士论文摘要库本论文所用的有机配体及缩写  V本论文所用的有机配体及缩写 OHNOOHOHOHNOOHOHClClOHNOHOHOHOClCl(S,E)-4-(2-hydroxybenzylideneamino)-2-hydroxybutanoic acid  (H3L1)(S,E)-4-(1-(3,5-dichloro-2-hydroxyphenyl)ethylideneamino)-2-hydroxybutanoic acid(H3L2)(E)-2-((2,3-dihydroxypropylimino)methyl)phenol(rac-H3L3)1-(3,5-dichloro-2-hydroxyphenyl)ethanone(Hdhap)         厦门大学博硕士论文摘要库Degree papers are in the “Xiamen University Electronic Theses and Dissertations Database”. Fulltexts are available in the following ways: 1. If your library is a CALIS member libraries, please log on http://etd.calis.edu.cn/ and submitrequests online, or consult the interlibrary loan department in your library. 2. For users of non-CALIS member libraries, please mail to etd@xmu.edu.cn for delivery details.厦门大学博硕士论文摘要库

Synthesis，Structures and Properties of Chiral Polymetallic Clusters

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Synthesis，Structures and Properties of Chiral Polymetallic Clusters

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