赵颖隽
论文题目：新型含氮、硫、氧配体及其超分子化合物的设计合成
作者简介：赵颖隽，女，1975年05月出生，1997年09月师从于中国科学院福建物质结构研究所洪茂椿教授，于2002年08月获博士学位。
摘
要
过渡金属与多官能团配体通过配位键来驱动和引导自组装形成具有均一尺寸和特定形状的金属-有机纳米器件是当今化学与材料领域研究的前沿之一。而通过设计合成具有特定对称性和立体选择性的有机配体，并把它们与金属离子自组装形成具有纳米尺寸和特殊功能的纳米球和纳米管更是在纳米科技、化学催化、分子吸附和光电磁等领域具有重要的科学意义和应用前景。
本论文以结构化学指导新型金属-有机纳米器件的合理合成和物理性能研究，探索它们的自组装规律，共设计合成了12个含N、S及COO-基团的具有不同对称性和立体选择性的新颖大骨架多官能团柔性配体，以及由它们与金属离子自组装合成了18个新型金属-有机纳米笼、纳米管和配位聚合物，开辟了一条合成金属-有机纳米器件的新途经。其中，一个具有Oh对称的金属纳米笼，笼内体积超过1000Å3，可以同时容纳多种离子和小分子，是目前已测定单晶结构的金属纳米笼中容量最大的一个；而用金属离子把纳米管串联成的金属-有机纳米管则是国际上首例报道的结构有序无机-有机纳米管阵列；本论文还创新性的采用低温溶剂热法合成了一个新颖的具有半导体和顺磁性质的Ni-巯基嘧啶二维层状聚合物和两个二维折叠格子状化合物；另外，用巯基嘧啶作为难溶盐CuCN溶解模板，得到了国际上首例的六角形CuCN大环化合物和另外一个新颖的类石墨层状CuCN化合物。
第一部分：文献综述
介绍了超分子化学、自组装、晶体工程等概念和配位超分子化合物的应用意义，从点阵结构和环状结构两方面，系统地综述了配位化学中的超分子结构类型，最后介绍了含N、S配体的设计合成思想。
第二部分：含N, S配体的设计合成与相关金属超分子化合物
本部分用含N, S的简单配体与含苄基溴的有机化合物反应合成了9个具有不同对称性、立体选择性的新颖的大骨架多官能团配体，与不同金属离子通过自组装反应，得到了11个结构新颖的化合物，它们是目前国际上已测定单晶结构的容量最大的金属纳米笼[Ni6(tpst)8Cl12]·24DMF·13H2O、首例结构有序一维纳米管阵列无机-有机聚合物[Ag7(tpst)4(ClO4)2(NO3)5(DMF)2]n、一维螺旋链化合物[Ag2(ppsp)2(NO3)2]n和[Ag2(mpsp)2(NO3)2]n、三十员双核大环状化合物[Ag2(psb)2(ClO4)2]、Z字型链化合物[Ag(psmq)ClO4]n；双银原子链化合物 [Ag2(bbch)2(NO3)2]n、单核化合物[Ag(bbch)2](ClO4)；双核银S形环化合物 [Ag2(mpst·H+)2(ClO4)4(DMF)2(CH3OH)2]n、双核铜环形化合物[Cu2(pmse)2Cl4]以及层状化合物[Ag(tmpt) (DMF)2(ClO4)]n。
第三部分：含N,S,COO‑的配体合成及相关化合物结构
该部分创新性地设计合成了两个新颖的含有吡啶和苯羧酸两种混合官能团单元并具有很好柔性和长度的配体spcp-和m-spcp-，与Ni2+和Cu2+在低温溶剂热反应条件中得到了两个二维折叠格子状化合物[Ni(spcp)2]n 和[Cu(spcp)2(H2O)]n.(H2O)2n，并对它们的单晶结构及磁性进行了研究。另外还利用配体spmp- 作为获得巯基嘧碇配体的前驱体与Ni(OAc)2在溶剂热条件下反应，得到了一个类石墨二维层状化合物[Ni2(C4H3N2S)4]n，该化合物具有很好的半导体性质和顺磁性质。
第四部分：CuCN系列化合物研究
由于具有许多特殊的性能，金属-氰化合物的研究是当今化学研究的热点之一。本工作创新性地采用2-巯基嘧啶作为溶解CuCN的模板，再与PPh3, PPh4Br, 2,2’-bpy等配体反应，得到了三个新颖的CuCN化合物，分别为二维的石墨层状化合物[(PPh4){Cu2(CN)3}]n、国际上首例六员大环化合物[Cu(CN)(PPh3)]6、一维树枝状化合物[Cu2(CN)2(PPh3)(2,2’-bpy)(DMSO)]n；以及巯基嘧啶直接与CuCN反应分离得到的六核铜簇合物[Cu6(pmdy)6(DMF)2]。
第五部分：发表文章，科研成果及奖励情况
本工作共发表SCI论文11篇，具中影响因子2.70 以上的五篇代表作：1、J. Am. Chem. Soc., 2000, 122, 4819-4820 （Maochun Hong,* Yingjun Zhao et al，Nanometer-Sized Metallosupramolecular Cube with Oh Symmetry）；2、Angew. Chem. Int. Ed., 2000, 39, 2468-2470 (Maochun Hong,* Yingjun Zhao et al，A Silver (I) Coordination Polymer Chain Containing Nanosized Tubes with Anion and Solvent Molecular Guests )；3、Chem. Commun., 2001, 1020-1021 （Yingjun-Zhao, Maochun-Hong,* et al, A paramagnetic lamellar polymer with a high semiconductivity）；4、J. Chem. Soc. Dalton Trans. 2000, 1685-1686 (Yingjun-Zhao, Maochun-Hong,* et al, Synthese and Structure Characterization of a Series of Cu-CN Compounds with Cu6 Unit)；5、J. Chem. Soc. Dalton Trans. 2000, 1685-1686 (Yingjun-Zhao, Maochun-Hong, * et al, A coordination polymer containing puckered square-like grids)。除上述5篇文章外，还有6篇本人为第一作者的文章发表在国际SCI杂志上，另外还与本组同事合作共发表论文11篇。
截止到2002年3月，发表的论文Angew. Chem.Int. Ed., 2000, 39, 2468-2470.和J. Am. Chem. Soc., 2000, 122, 819-4820.共被国内外同行引用18次；德国Albert-Ludwigs 大学化学系H. Vahrenkamp教授认为我们有关金属-氰聚合物工作（J. Chem. Soc. Dalton Trans. 2000, 1685-1686）是非常出色的研究工作，并邀请我们为他的丛书Inorganic Syntheses撰稿。
2001年度中国科学院自然科学奖一等奖“新型无机聚合物的设计合成、结构规律与性能研究” 共有36个完成人，本人排名第七（前面6名均为在职人员）。由本论文所合成的纳米管状化合物被收录在香港中文大学Mak教授主编的《高等无机结构化学》第五章（5.5.3分子多边形和分子管）一节中。另外，还获得过中国科学院院长奖学金、中国科学院宝钢教育基金、刘永龄奖学金等多项奖励。
关键词：配位超分子化合物，自组装，大骨架，多官能团，设计合成
Abstract
Studies on the nano-scale coordination supramolecules, especially coordination nano-ball and nano-tube molecules, constructed by transition metals and ligands with multi-functional groups through coordination bonds are of great interest, because they are of great importance in the application in nano-technology catalysis, absorption, optical, electrical, and magnetic fields. These supramolecular compounds are usually built via spontaneous aggregation of constituent subunits in the reaction systems, thus the selection of ligands and metal ions along with the control of reaction conditions plays key roles.
Based on the principle of structural chemistry, rational syntheses, self-assembly rule and properties of novel metal-organic nano-devices are investigated in this work, of which，twelve novel nitrogen-, thiolate- or carboxylate- containing soft ligands with different symmetry and stereochemical preferences were designed and synthesized. And eighteen novel coordination supramolecular complexes have been constructed and characterized. The highlights of this thesis are following: the largest coordination cube-like molecular nano-cage with a volume of more than 1000 Å3 was obtained from multi-solvent system, the cage can accommodate various kinds of small guest ions or molecules that can go in and out the cage freely; the first ordered inorganic-organic array of coordination polymer constructed by nano-meter sized tubes was isolated; a novel 2D Ni-mercapto pyrimidine compound possessing semi-conducting and para-magnetic properties along with two novel 2D puckered grid-like compounds were synthesized by low-temperature solvo-thermal method; and the first hexagonal CuCN complex and a novel graphite-like CuCN complex were generated in the presence of auxiliary ligands and pmdy template.
Part I：Review on the Self-assembly Supramolecules in Coordination Chemistry
The concepts of supramolecules, self-assembly and crystal engineering and the importance of coordination supramolecules were introduced; A systematically review on the structural types of supramolecules in coordination chemistry were made. The design of new nitrogen- and sulfur- containing ligands was also introduced.
Part II: Design and Synthesis of New Nitrogen- and Sulfur- Containing Ligands and Their Metal Supramolecular Complexes
Nine novel ligands have been designed and synthesized. In the self-assembly of these ligands with different metal salts, eleven new supramolecular complexes have been synthesized and characterized by X-ray single-crystal diffraction analysis，they are: the largest nano-scale molecular cage complex [Ni6(tpst)8Cl12]·24DMF·13H2O, the first inorganic-organic array 1D coordination polymer [Ag7(tpst)4(ClO4)2(NO3)5(DMF)2]n constructed by nano-scale tube, 1D helical chain-like complexes [Ag2(ppsp)2(NO3)2]n and [Ag2(mpsp)2(NO3)2]n, thirty-membered dinuclear silver ring [Ag2(psb)2(ClO4)2], zigzag chain-like complex [Ag(psmq)ClO4]n, double chain complex [Ag2(bbch)2(NO3)2]n, mononuclear complex [Ag(bbch)2](ClO4), dinuclear S-like ring [Ag2(mpst·H+)2(ClO4)4(DMF)2 (CH3OH)2, dinuclear copper ring [Cu2(pmse)2Cl4], and 2D layer structure [Ag(tmpt) (DMF)2(ClO4)]n.
Part III: Design and Synthesis of Nitrogen- Sulfur- and Carboxylate- Containing Ligands and the Structures of Their Related Complexes
Two novel long and soft ligands, spcp- and m-spcp-, with hybrid pyridine and carboxylate groups have been designed and synthesized, two novel 2D complexes [Ni(spcp)2]n and [Cu(spcp)2(H2O)]n.(H2O)2n with puckered grids have been successfully obtained under solvo-thermal condition. However the other ligand spmp- decomposed in the reaction with Ni2+ under low-temperature solvo-thermal condition and resulted in a 2D graphite-like complex [Ni2(C4H3N2S)4]n, which shows ferromagnetic interaction between the nickel(II) centers and possesses semi-conducting property.
Part IV: Studies on Copper Cyanide Complexes
The cyanide complexes are of great interest in their rich electrical and magnetic properties, of which, copper cyanide attracts many chemists because no definite structure have been found due to its poor solubility till now. Under the presence of pmdy, the reaction of CuCN and PPh4Br, PPh3, 2,2’-bpy yielded three copper cyanide complexes, 2D graphite-like lamellar [(PPh4){Cu2(CN)3}]n, the first discrete hexagonal cavity framework [Cu(CN)(PPh3)]6, and one-dimensional branch-like structure [Cu2(CN)2(PPh3)(2,2’-bpy)(DMSO)]n. However, when CuCN was directly reacted with pmdy, hexanuclear complex [Cu6(pmdy)6(DMF)2] was isolated.
Part V: Publications and Awards
Eleven papers have been published, including five high-quality papers [J. Am. Chem. Soc., 2000, 122, 4819-4820 （Maochun Hong,* Yingjun Zhao et al，Nanometer-Sized Metallosupramolecular Cube with Oh Symmetry）； Angew. Chem. Int. Ed., 2000, 39, 2468-2470 (Maochun Hong,* Yingjun Zhao et al，A Silver (I) Coordination Polymer Chain Containing Nanosized Tubes with Anion and Solvent Molecular Guests )；Chem. Commun., 2001, 1020-1021 （Yingjun-Zhao, Maochun-Hong,* et al, A paramagnetic lamellar polymer with a high semiconductivity）; J. Chem. Soc. Dalton Trans. 2000, 1685-1686 (Yingjun-Zhao, Maochun-Hong,* et al, Syntheses and Structure Characterization of a Series of Cu-CN Compounds with Cu6 Unit); J. Chem. Soc. Dalton Trans. 2000, 1685-1686 (Yingjun-Zhao, Maochun-Hong,* et al, A coordination polymer containing puckered square-like grids)] and other six papers published in SCI journals. Besides, other 11 co-author papers have been published.
Till March, 2002, the papers Angew. Chem.Int. Ed., 2000, 39, 2468-2470. and J. Am. Chem. Soc., 2000, 122, 819-4820 have been cited 18 times by others. Prof. H. Vahrenkamp from chemsity department of Albert-Ludwigs University gave high evaluation on the paper entitled Synthese and Structure Characterization of a Series of Cu-CN Compounds with Cu6 Unit, J. Chem. Soc. Dalton Trans. 2000, 1685-1686 and invited us to contribute a chapter to his book Inorganic Syntheses.
In 2001, the design, syntheses, structures and the properties of novel inorganic polymers won the First-Class Award for Natural Science of Chinese Academy of Sciences. There are thirty-six participants in the award, where I ranked seventh (the first six are staff). The nano-tube complex synthesized in this thesis has been embodied in 《Advanced Inorganic Chemitry 》Chapter five (5.5.3 Molecular Polygon and Molecular Tube). Meanwhile, I also obtained several awards, such as The Fellowship of Dean of Chinese Academy of Sciences, BaoGang and LiuYongLing Scholarship of Chinese Academy of Sciences and First-Class Awards of Fujian Institute of Research on the Structure of Matter.
Keywords: coordination supramolecular complex, self-assembly, multi-functional group, design and synthesis
