桥联多核金属配合物的制备与性质研究
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摘要
本文研究的主要内容是氧桥联过渡金属簇合物的合成、结构和性质研究。我们选用了杂环酸(2-苯基-1,2,3-三氮唑-4-甲酸、L-噻唑烷基4-甲酸2,3,4,5-四氟邻苯二甲酸)、水杨醛及其希夫碱类衍生物、邻羟基苯乙酮及其衍生物等作为配体,采用室温挥发法、试管扩散法共合成了24个新型配位化合物,分别用红外和元素分析进行了表征,并用X-射线单晶衍射解析了它们的晶体结构,还研究了部分配位聚合物的磁学性质和电化学性质。
1.用2-苯基-1,2,3-三氮唑-4-甲酸、L-噻唑烷基4-甲酸2,3,4,5-四氟邻苯二甲酸、咪唑、2,2′-联吡啶等作为桥联配体,组装了10个过渡金属配合物。这三种杂环酸展现了丰富的配位模式,由于官能团的位置以及杂环原子种类的不同,它们在形成配位聚合物时所起的作用不同。四氟邻苯二甲酸通常能够组装出一维和二维结构,咪唑分子既可以作为配位原子参与配位,也可以作为具有缓冲性质的碱而脱掉羧酸上的质子,从而促进羧基与过渡金属配位。2,2′-联吡啶的配位阻碍了更高维数结构的形成,但是它容易形成分子间C—H…O氢键和π-π堆积作用,从而促进了超分子结构的形成。
2.由水杨醛、5-氯水杨醛、邻羟基苯乙酮及5-甲基-2-羟基苯乙酮作为配体与醋酸镍组装出了4个氧(包括酚羟基氧子和烷氧基氧原子)桥联簇合物。这四种配体借助于自身的两种氧和来自溶剂的水分子、甲醇分子共同与金属镍配位组装出类似立方烷结构的四核镍金属簇合物。
3.由邻香草醛缩L-丁醇胺与3,5-二溴水杨醛缩乙醇胺与醋酸锰自组装出了两个三核锰簇合物,邻香草醛缩乙醇胺与镍、铜离子组装出四核铜、镍的簇合物。配体通过自身的配位原子并且借助于醋酸根离子、溶剂甲醇以及水分子共同桥联过渡金属离子而配合生成多核簇合物。
4.由水杨醛类希夫碱与过渡金属离子配合分别组装出了L-锰(单核)、L-钴(通过水分子与配合物间的氢键连接成为一维链状)、L-铜(双核铜通过氢键连接为一维链状结构)、L-镍(双核);由邻羟基苯乙酮缩乙醇胺与铜离子组装出四核铜的簇合物,具有类似金刚烷结构。
This dissertation mainly includes synthesis,structures and properties of new transition metal coordination clusters.We selected heterocyclic acids(including 2-phenyl-2H-1,2,3-triazole-4-carboxylic acid,thiazolidine-2-carboxylic acid, 3,4,5,6-tetrafluorophthalic acid),salicylaldehyde and the derivatives of Salicylaldehyde Schiff base,1-(2-hydroxyphenyl)ethanone and the derivatives of 1-(2-hydroxyphenyl)ethanone as ligands to synthesize 24 new coordination compounds though Volatiling at room temperature and tube diffusing.These complexes were characterized by FT-IR,elemental analysis and X-ray crystallography.Magnetic properties and electrochemical properties of several coordination compounds were studied.
1.10 new transition metal coordination compounds were assembled by using 2-phenyl-2H-1,2,3-triazole-4-,thiazolidine-2-carboxylic acid,3,4,5,6-tetrafluorophthalic acid, imidazole and 2,2'-pyridine as bridging ligands and transition metals.These three heterocyclic acids have versatile coordination modes.Owing to the different persition of functional groups(carboxyl groups)and the difference of miscellaneous types of atoms,they had different effacts when coordinating to the metal ions.3,4,5,6-tetrafluorophthalic acid can usually assembly 1-D and 2-D structures.Imidazole can coordinate to the transition metal ions as well as base having buffering capability which can absorb proton coming from carboxyl,and it promoted carboxylic acid coordinating to the transition metal ions.2,2'-pyridine lowers the tendency of formation of metal complexes with high-dimensional structures.But 2,2'-pyridine is liable to form C—H...O hydrogen bonds andπ-πinteractions which may form supramolecular structure.
2.Salicylaldehyde,5-chloro-2-hydroxybenzaldehyde,1-(2-hydroxyphenyl)ethanone and 1-(2-hydroxy-5-methylphenyl)ethanone can coordinate to nickel ion as lingands to form four nuclear nickle cluster complexes.These four ligands with two sorts of oxygen atoms can coordinate to the meatl ions with the help of solvent molecules such as H_2O and CH_3OH and so on to form similary to cubane structure.
3.2-((1-hydroxy-2- methylpropan-2-ylimino)methyl)-6-methoxyphenol and 2,4-dibromo-6-((2-hydroxyethylimino)methyl)phenol as ligands coordinate to manganese ion to form three nuclear cluster complexes.Four nuclear clusters of nickle and copper were assemled by using 2-((2-hydroxyethylimino)methyl)-6-methoxyphenol as bridged ligands.
4.Salicylaldehyde Schiff base ligands coordinated to transition metal ions to form L-Mn(Ⅱ)(single nuclear),L-Co(Ⅱ)(one-dimensional structure linked by H_2O molecular), L-Cu(Ⅱ)(double-nuclear complex linked by hydrogen bonds into one-dimensional chain structure),L-Ni(double-nuclear).Four nuclear copper complex was assembled by 2-((2-hydroxyethylimino)methyl)phenol ligand and copper ions.
1.用2-苯基-1,2,3-三氮唑-4-甲酸、L-噻唑烷基4-甲酸2,3,4,5-四氟邻苯二甲酸、咪唑、2,2′-联吡啶等作为桥联配体,组装了10个过渡金属配合物。这三种杂环酸展现了丰富的配位模式,由于官能团的位置以及杂环原子种类的不同,它们在形成配位聚合物时所起的作用不同。四氟邻苯二甲酸通常能够组装出一维和二维结构,咪唑分子既可以作为配位原子参与配位,也可以作为具有缓冲性质的碱而脱掉羧酸上的质子,从而促进羧基与过渡金属配位。2,2′-联吡啶的配位阻碍了更高维数结构的形成,但是它容易形成分子间C—H…O氢键和π-π堆积作用,从而促进了超分子结构的形成。
2.由水杨醛、5-氯水杨醛、邻羟基苯乙酮及5-甲基-2-羟基苯乙酮作为配体与醋酸镍组装出了4个氧(包括酚羟基氧子和烷氧基氧原子)桥联簇合物。这四种配体借助于自身的两种氧和来自溶剂的水分子、甲醇分子共同与金属镍配位组装出类似立方烷结构的四核镍金属簇合物。
3.由邻香草醛缩L-丁醇胺与3,5-二溴水杨醛缩乙醇胺与醋酸锰自组装出了两个三核锰簇合物,邻香草醛缩乙醇胺与镍、铜离子组装出四核铜、镍的簇合物。配体通过自身的配位原子并且借助于醋酸根离子、溶剂甲醇以及水分子共同桥联过渡金属离子而配合生成多核簇合物。
4.由水杨醛类希夫碱与过渡金属离子配合分别组装出了L-锰(单核)、L-钴(通过水分子与配合物间的氢键连接成为一维链状)、L-铜(双核铜通过氢键连接为一维链状结构)、L-镍(双核);由邻羟基苯乙酮缩乙醇胺与铜离子组装出四核铜的簇合物,具有类似金刚烷结构。
This dissertation mainly includes synthesis,structures and properties of new transition metal coordination clusters.We selected heterocyclic acids(including 2-phenyl-2H-1,2,3-triazole-4-carboxylic acid,thiazolidine-2-carboxylic acid, 3,4,5,6-tetrafluorophthalic acid),salicylaldehyde and the derivatives of Salicylaldehyde Schiff base,1-(2-hydroxyphenyl)ethanone and the derivatives of 1-(2-hydroxyphenyl)ethanone as ligands to synthesize 24 new coordination compounds though Volatiling at room temperature and tube diffusing.These complexes were characterized by FT-IR,elemental analysis and X-ray crystallography.Magnetic properties and electrochemical properties of several coordination compounds were studied.
1.10 new transition metal coordination compounds were assembled by using 2-phenyl-2H-1,2,3-triazole-4-,thiazolidine-2-carboxylic acid,3,4,5,6-tetrafluorophthalic acid, imidazole and 2,2'-pyridine as bridging ligands and transition metals.These three heterocyclic acids have versatile coordination modes.Owing to the different persition of functional groups(carboxyl groups)and the difference of miscellaneous types of atoms,they had different effacts when coordinating to the metal ions.3,4,5,6-tetrafluorophthalic acid can usually assembly 1-D and 2-D structures.Imidazole can coordinate to the transition metal ions as well as base having buffering capability which can absorb proton coming from carboxyl,and it promoted carboxylic acid coordinating to the transition metal ions.2,2'-pyridine lowers the tendency of formation of metal complexes with high-dimensional structures.But 2,2'-pyridine is liable to form C—H...O hydrogen bonds andπ-πinteractions which may form supramolecular structure.
2.Salicylaldehyde,5-chloro-2-hydroxybenzaldehyde,1-(2-hydroxyphenyl)ethanone and 1-(2-hydroxy-5-methylphenyl)ethanone can coordinate to nickel ion as lingands to form four nuclear nickle cluster complexes.These four ligands with two sorts of oxygen atoms can coordinate to the meatl ions with the help of solvent molecules such as H_2O and CH_3OH and so on to form similary to cubane structure.
3.2-((1-hydroxy-2- methylpropan-2-ylimino)methyl)-6-methoxyphenol and 2,4-dibromo-6-((2-hydroxyethylimino)methyl)phenol as ligands coordinate to manganese ion to form three nuclear cluster complexes.Four nuclear clusters of nickle and copper were assemled by using 2-((2-hydroxyethylimino)methyl)-6-methoxyphenol as bridged ligands.
4.Salicylaldehyde Schiff base ligands coordinated to transition metal ions to form L-Mn(Ⅱ)(single nuclear),L-Co(Ⅱ)(one-dimensional structure linked by H_2O molecular), L-Cu(Ⅱ)(double-nuclear complex linked by hydrogen bonds into one-dimensional chain structure),L-Ni(double-nuclear).Four nuclear copper complex was assembled by 2-((2-hydroxyethylimino)methyl)phenol ligand and copper ions.
引文
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[3] (a) Bruce D. W., Hare(ed) D.O., Inorganic Materials, 2nde. John Wiley&Sons, New York,1996.
(b) Day.P., Coord. Chem.Rev., 1999,190-192,827.
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(d) Kahn O., Molecular Magnetism, NewYork:VCH Publishers, 1993.
[4] (a) Battern S.R., Robson R., Angew. Chem. Int.Ed.,1998,38,1405.
(b) Battern S.R., Hoskins B.F.,Moubaraki B., Muyyay K. S., Robson R., Chem. Commun., 2000,195.
(c) Desiraju G.R., Chem. Commun., 1997,1475.
(d) Goodgame D. M. L, Garchvogel D. J., Angew.Chem. Int.Ed., 1999,38,153.
(e) Pan L. Ching N., Huang X.Y., Chem. Eur. J., 2001,7,4431
[5] Braga,D., Chem. Commun., 2003,2751
[6] (a) Fujita M, Chem.Soc. Rev., 1998,27,217
(b) Yaghi O.M., Li H., Davis C.,Coord. Chem.Rev., 1999,183,
(c) Braga D., Coord. Chem.Rev., 1999,183,19,
(d) Sweiegers G. F., Malefetse T. J., Chem.Rev.,2000,100,3483,
(e) Moulton B. Zaworotko M. J, Chem.Rev.,2001,101,1629
(f) Holingsworth M. D, Sceience, 2002,29,2410.
(g) Seidel S. R.,Stang P. J., Acc.Chem. Res., 2002,35, 972
(h) Evans O.R., Lin W. B., Acc.Chem. Res., 2002,35,511.
[7]Alekseyeva E. S., Batsanov A. S., Boyd L. A., Dalton. Trans.,2003,475
[8] Abermethy C. D., Macdonald C. L. B, Chem. Commun., 2001, 61.
[9] Devic T., Evain M., J.Am.Chem.Soc.,2003,125,3295.
[10] Khlobystov A. N. Blake A.J., Chamoness N.r., Coord. Chem.Rev.,2001,222,155.
[11] Pullen A. E., Olk R. M., Coord. Chem. Rev, 1999,188,211.
[12]Che C. M., Mao Z/, Miskowski V. M., Tse M. C., Chan C. K., Cheung K. K Phillips D. L, Leung K. H, Angew. Chem. Int. Ed, 2000, 39,4084.
[13]Moulton B, Zaworotko M. J, Chem. Rev, 2001, 101, 1629.
[14]Kondo M, Yoshitomi T, Seki K, Matsuzaka H, Kitagawa S., Angew. Chem. Int. Ed.Engl, 1997,36,1725.
[15]Sharma C. V. K, Rogers R. D, Chem. Comrnun, 1999, 83.
[16]Robinson F., Zaworotko M. J., J. Chem. Soc. Chem. Commun, 1995,2413.
[17]洪茂椿, 陈荣,梁文平,21世纪的无机化学,科学出版社, 2005.
[18]Biradha K., Domasevitch K. V, Moulton B, Seward C, Zaworotko M. J, Chem. Commun, 1999,1327.
[19]Biradha K., Fujita M., J. Chem. Soc., Dalton Trans, 2000, 3805.
[20]Biradha K., Hongo Y., Fujita M., Angew. Chem. Int. Ed, 2000, 39, 3843.
[21](a) Chui S. S-Y., Lo S. M-F., Charmant J. P. H, Science, 1999, 283,1148-1150.
(b) Yaghi O. M., Davis C. E., Li G., J. Am. Chem. Soc., 1997, 119, 2861-2868.
(c)Choi H. J., Suh M. P., J. Am. Chem. Soc., 1998,120,10622-10628.
(d) Plater M. J., Forema M. R., Howei R. A, Inorg. Chim. Acta, 2001, 319,159-175.
[22] (a) Wang S., Hu M. L., Yuan J. X., Chin. J. Chem., 2000,18, 546-550.
(b) Wu C. D., Lu C. Z., Wu D. M., Inorg. Chem. Commun., 2001,4, 561 — 564.
(c) Plater M. J., Forema M. R., Howei R A, Inorg. Chim. Acta, 2001, 315,126-132.
(d) Wu C. D., Lu C. Z., Lu S. F., Inorg. Chem. Commun., 2002, 5, 171 — 174.
(e) Cao R., Sun D., Liang U., Inorg. Chem, 2002, 41, 2087-2094.
[23]Rico E., Sesto D, Arif A. M., Miller S. J, Inorg. Chem, 2000, 39,4894.
[24] Bourne S. A, Lu J. J, Mondal A, Moulton B, Zaworotko M. J., Angew. Chem, Int. Ed, 2001, 40,2111.
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