以Schiff base为配体的Cu(Ⅱ)-金属凝胶的制备和表征

doi:10.11944/j.issn.1000-0518.2016.07.150382

摘要/Abstract

摘要：

以间苯二甲醛分别与异烟肼、烟酸酰肼和2-吡啶甲酰肼反应,合成了3种含吡啶环的Schiff base配体间苯二甲醛双缩4-吡啶甲酰腙(S1)、间苯二甲醛双缩3-吡啶甲酰腙(S2)和间苯二甲醛双缩2-吡啶甲酰腙(S3);测试了这3个化合物与醋酸铜通过配位作用在不同溶剂中形成金属凝胶的能力,结果发现,配体S1与醋酸铜在DMF/H₂O和DMSO/H₂O的混合溶剂中、配体S3与醋酸铜在DMF/H₂O的混合溶剂中均可以形成金属凝胶。胶凝测试结果表明,吡啶环上N原子位置的不同,对化合物形成金属凝胶的能力有极大影响。利用扫描电子显微镜(SEM)观察了金属凝胶的微观形貌,结果表明,配体分子的结构对金属凝胶的微观形貌也有较大影响;红外光谱和紫外可见光谱的研究证明了配位作用在金属凝胶形成过程中的推动作用;X射线衍射分析(XRD)研究表明,配体S1与醋酸铜在两种混合溶剂中形成的金属凝胶均表现出了四方堆积结构。

关键词: 金属凝胶, Schiff base配体, 配位作用, 自组装

Abstract:

Three Schiff base ligands containing two pyridine rings, isophthalaldehyde-bis(4-pyridine formyl hydrazone)(S1), isophthalaldehyde-bis(3-pyridine formyl hydrazone)(S2) and isophthalaldehyde-bis(2-pyridine formyl hydrazone) (S3), have been synthesized with isophthalaldehyde and one of isonicotinyl hydrazine, nicotinic hydrazine and 2-pyridine-carboxylic acid hydrazine as raw materials. The gelation behaviors of the three Schiff base ligands with Cu(Ac)₂ in different solvents were tested, and three Cu(Ⅱ)-metallogels were obtained. The gelation test results show that a slight variation in ligand structures can lead to dramatic changes in gelation abilities of ligands. The microstructures of metallogels observed by SEM reveal that the morphology of a metallogel depends on the structure of the ligand. FT-IR and UV/Vis spectroscopy studies reveal that the coordination interaction between Schiff base ligands and Cu(Ⅱ) plays an important role for the formation and maintenance of metallogels. The XRD analysis demonstrates that two metallogels formed by ligand S1 and Cu(Ac)₂ in two mixed solvents take the same tetragonal packing mode.

Key words: metallogel, Schiff base ligands, coordination interaction, self-assembly

薛敏, 冯延安, 刘振, 孙平. 以Schiff base为配体的Cu(Ⅱ)-金属凝胶的制备和表征[J]. 应用化学, 2016, 33(7): 804-812.

XUE Min, FENG Yanan, LIU Zhen, SUN Ping. Cu(Ⅱ)-Coordinated Supramolecular Metallogels Based on Schiff Base Ligands: Preparation and Characterization[J]. Chinese Journal of Applied Chemistry, 2016, 33(7): 804-812.

参考文献

[1]	Whitesides G M,Grzybowski B. Self-Assembly at All Scales[J]. Science,2002,295(29):2418-2421.
[2]	Yan N,Xu Z Y,Diehn K K,et al.How Do Liquid Mixtures Solubilize Insoluble Gelators? Self-Assembly Properties of Pyrenyl-Linker-Glucono Gelators in Tetrahydrofuran Water Mixtures[J]. J Am Chem Soc,2013,135(24):8989-8999.
[3]	Sangeetha N M,Maitra U. Supramolecular Gels: Functions and Uses[J]. Chem Soc Rev,2005,34(10):821-836.
[4]	Terech P,Weiss R G. Low Molecular Mass Gelators of Organic Liquids and the Properties of Their Gels[J]. Chem Rev,1997,97(8):3133-3160.
[5]	Yagai S,Nakajima T,Kishikawa K,et al.Hierarchical Organization of Photoresponsive Hydrogen-Bonded Rosettes[J]. J Am Chem Soc,2005,127(31):11134-11139.
[6]	Lee H,Jung S H,Han W S,et al.A Chromo-Fluorogenic Tetrazole-Based CoBr2 Coordination Polymer Gel as a Highly Sensitive and Selective Chemosensor for Volatile Gased Containing Chloride[J]. Chem-Eur J,2011,17(10):2823-2827.
[7]	Beck J B,Rowan S J. Multistimuli, Multiresponsibe Metallo-Supramolecular Polymers[J]. J Am Chem Soc,2003,125(46):13922-13923.
[8]	Kishimura A,Yamashita T,Aida T. Phosphorescent Organogels via “Metallophilic” Interactions for Reversible RGB-Color Switching[J]. J Am Chem Soc,2005,127(1):179-183.
[9]	Van Bommel K J C,Stuart M C A,Feringa B L,et al. Two-stage Enzyme Mediated Drug Release from LMWG Hydrogels[J]. Org Biomol Chem,2005,3(16):2917-2920.
[10]	Vemula P K,Li J,John G. Enzyme Catalysis:Tool to Make and Break Amygdalin Hydrogelators from Renewable Resources:A Delivery Model for Hydrophobic Drugs[J]. J Am Chem Soc,2006,128(27):8932-8938.
[11]	Rodríquez-Liansola F,Miravet J F,Escuder B. A Supramolecular Hydrogel as a Reusable Heterogeneous Catalyst for the Direct Aldol Reaction[J]. Chem Commun,2009,(47):7303-7305.
[12]	Kawan S I,Tamaru S I,Fujita N,et al.Sol-Gel Polycondensation of Tetraethyl Orthosilicate(TEOS) in Sugar-Based Porphyrin Organogels:Inorganic Conversion of a Sugar-Directed Porphyrinic Fiber Library through Sol-Gel Transcription Processes[J]. Chem-Eur J,2004,10(2):343-351.
[13]	Chen J,Yoshida M,Maekawa Y,et al.Temperature-Switchable Vapor Sensor Materials Based on N-isorpopylacrylamide and Calcium Chloride[J]. Polymer,2001,42(23):9361-9365.
[14]	Piepenbrock M M,Lloyd G O,Clarke N,et al.Metal- and Anion-Binding Supramolecular Gels[J]. Chem Rev,2010,110(4):1960-2004.
[15]	Tam A Y Y,Yam V W W. Recent Advances in Metallogels[J]. Chem Soc Rev,2013,42(4):1540-1567
[16]	CHEN Kai,JIN Xin,TANG Liming. Supramolecular Metallogels[J]. Prog Chem,2010,22(6):1094-1101(in Chinese). 陈凯,金鑫,唐黎明. 超分子金属凝胶[J]. 化学进展,2010,22(6),1094-1101.
[17]	WEN Xing,TANG Liming,LIN Wanxin. Fabrication of Environmental Responsive Copolymer One-dimensional Nanostructures Using Metallogel Fibers as Template[J]. Chem J Chinese Univ,2015,36(1):180-187(in Chinese). 温幸,唐黎明,林晚心. 以金属凝胶纤维为模板制备环境响应型共聚物一维纳米结构[J]. 高等学校化学学报,2015,36(1):180-187.
[18]	Zhang J J,Lu W, Sun R W Y, et al. Organogold(Ⅲ) Supramolecular Polymers for Anticancer Treatment[J]. Angew Chem Int Ed,2012,51(20):4882-4886.
[19]	Yan X Z,Xu D H,Chi X D,et al.A Multiresponsive, Shape-Presistent, and Elastic Supramolecular Polymer Network Gel Constructured by Orthogonal Self-Assembly[J]. Adv Mater,2012,24(3):362-369.
[20]	Au V K M,Zhu N Y,Yam V W W. Luminescent Metallogels of Bis-Cyclometalated Alkynylgold(Ⅲ) Complexes[J]. Inorg Chem,2013,52(2):558-567.
[21]	CHEN Siru,XUE Ming,PAN Ying,et al.Synthesis, Characterization and Gas Adsorption Properties of Two New Porous Metal-organic Gels[J]. Chem J Chinese Univ,2015,36(5):815-820(in Chinese). 陈思如,薛铭,潘莹,等. 两种新型多孔金属-有机凝胶的合成、表征与气体吸附性能[J]. 高等学校化学学报,2015,36(5):815-820.
[22]	Piepenbrock M O M,Clarke N,Steed J W. Rheology and Silver Nanoparticle Templating in a Bis(urea) Silver Metallogel[J]. Soft Matter,2011,7(6):2412-2418.
[23]	Kishida T,Fujita N,Sada K,et al.Sol-Gel Reaction of Porphyrin-Based Superstuctures in the Organogel Phase:Creation of Mechanically Reinforced Porphyrin Hybrids[J]. J Am Chem Soc,2005,127(20):7298-7299.
[24]	Kuroiwa K,Shibata T,Takada A,et al.Heat-Set Gel-like Networks of Lipophilic Co(Ⅱ) Trizaole Complexes in Organic Media and Their Thermochromic Structural Transitions[J]. J Am Chem Soc,2004,126(7):2016-2021.
[25]	Jin Q X,Zhang L,Cao H,et al.Self-Assembly of Copper(Ⅱ) Ion-Mediated Nanotube and Its Supramolecular Chiral Catalytic Behavior[J]. Langmuir,2011,27(22):13847-13853.
[26]	Banerjee S,Adarsh N N,Dastidar P. A Crustal Engineering Rationale in Designing a CdⅡ Coordination Polymer Based Metallogel Deribed from a C3 Symmetric Tris-amide-tris-carboxylate ligand[J]. Soft Matter,2012,8(29):7623-7629.
[27]	Hui J K H,Yu Z,MacLachlan M J. Supramolecular Assembly of Ainc Salphen Complexes: Access to Metal-Containing Gels and Nanofibers[J]. Angew Chem Int Ed,2007,46(42):7980-7983.
[28]	Wang W J,Chen Q H,Li Q,et al.Ligand-Structure Effect on the Formation of One-Dimensional Nanoscale Cu(Ⅱ)-Schiff Base Complexes and Solvent-Mediated Shape Transformation[J]. Cryst Growth Des,2012,12(5):2707-2713.
[29]	Whiteoak C J,Salassa G,Kleij A W. Recent Advances with π-Conjugated Salen Systems[J]. Chem Soc Rev,2012,41(2):622-631.
[30]	Xin Y,Yuan J Y. Schiff's Base as a Stimuli-responsive Linker in Polymer Chemistry[J]. Polym Chem,2012,3(11):3045-3055.
[31]	Andruh M. Compartmental Schiff-base Ligands-a Rich Library of Tectons in Designing Magnetic and Luminescent Materials[J]. Chem Commun,2011,47(11):3025-3042.
[32]	QIANG Lu,ZHU Jingying,TANG Liming,et al.Structure and Properties of an Organic Acylhydrazone Ligand and Its Metallogels[J]. Acta Polym Sin,2013,(3):414-418(in Chinese). 强璐,朱晶莹,唐黎明,等. 一种有机酰腙类配体及其金属凝胶的结构及性能[J]. 高分子学报,2013,(3):414-418.
[33]	Sengupta S,Mondal R. Elusive Nanoscale Metal-Organic-Particle-Supported Metallogel Formation Using a Nonconventional Chelating Pyridine-Pyrazole-Based Bis-Amide Ligand[J]. Chem-Eur J,2013,19(18):5537-5541.
[34]	Piepenbrock M M-O,Clarke N,Steed J W. Shear Induced Gelation in a Copper(Ⅱ) Metallogel: New Aspects of Ion-tunable Rheology and Gel-reformation by External Chemical Stimuli[J]. Soft Matter,2010,6(15):3541-3547.
[35]	Hu J S,Guo Y G,Liang H P,et al.Three-Dimensional Self-Organization of Supramolecular Self-Assembled Porphyrin Hollow Hexagonal Nanoprisms[J]. J Am Chem Soc,2005,127(48):17090-17095.
[36]	Yu C M,Xue M,Liu K,et al.Terthiophene Derivatives of Cholesterol-Based Molecular Gels and Their Sensing Application[J]. Langmuir,2014,30(5):1257-1265.