Citation: 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. doi: 10.11944/j.issn.1000-0518.2016.07.150382 shu

Cu(Ⅱ)-Coordinated Supramolecular Metallogels Based on Schiff Base Ligands: Preparation and Characterization

1.
The Key Laboratory for Surface Engineering and Remanufacturing in Shaanxi Province, School of Chemical Engineering, Xi'an Univeristy, Xi'an 710065, China

Corresponding author: XUE Min,
Received Date: 28 October 2015
Available Online: 15 January 2016
Fund Project:

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.
- metallogel,
- Schiff base ligands,
- coordination interaction,
- self-assembly
1. [1]
  [1] Whitesides G M,Grzybowski B. Self-Assembly at All Scales[J]. Science,2002,295(29):2418-2421.
2. [2]
  [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. [3]
  [3] Sangeetha N M,Maitra U. Supramolecular Gels: Functions and Uses[J]. Chem Soc Rev,2005,34(10):821-836.
4. [4]
  [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. [5]
  [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. [6]
  [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. [7]
  [7] Beck J B,Rowan S J. Multistimuli, Multiresponsibe Metallo-Supramolecular Polymers[J]. J Am Chem Soc,2003,125(46):13922-13923.
8. [8]
  [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. [9]
  [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. [10]
  [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. [11]
  [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. [12]
  [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. [13]
  [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. [14]
  [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. [15]
  [15] Tam A Y Y,Yam V W W. Recent Advances in Metallogels[J]. Chem Soc Rev,2013,42(4):1540-1567
16. [16]
  [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. [17]
  [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. [18]
  [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. [19]
  [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. [20]
  [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. [21]
  [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. [22]
  [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. [23]
  [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. [24]
  [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. [25]
  [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. [26]
  [26] Banerjee S,Adarsh N N,Dastidar P. A Crustal Engineering Rationale in Designing a Cd^Ⅱ Coordination Polymer Based Metallogel Deribed from a C3 Symmetric Tris-amide-tris-carboxylate ligand[J]. Soft Matter,2012,8(29):7623-7629.
27. [27]
  [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. [28]
  [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. [29]
  [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. [30]
  [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. [31]
  [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. [32]
  [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. [33]
  [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. [34]
  [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. [35]
  [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. [36]
  [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.
1. [1]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
2. [2]
  Ruoxi Sun , Yiqian Xu , Shaoru Rong , Chunmiao Han , Hui Xu . The Enchanting Collision of Light and Time Magic: Exploring the Footprints of Long Afterglow Lifetime. University Chemistry, 2024, 39(5): 90-97. doi: 10.3866/PKU.DXHX202310001
3. [3]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
4. [4]
  Wenjian Zhang , Mengxin Fan , Wenwen Fei , Wei Bai . Cultivation of Critical Thinking Ability: Based on RAFT Polymerization-Induced Self-Assembly. University Chemistry, 2025, 40(4): 108-112. doi: 10.12461/PKU.DXHX202406099
5. [5]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
6. [6]
  Tao Yu , Vadim A. Soloshonok , Zhekai Xiao , Hong Liu , Jiang Wang . Probing the dynamic thermodynamic resolution and biological activity of Cu(Ⅱ) and Pd(Ⅱ) complexes with Schiff base ligand derived from proline. Chinese Chemical Letters, 2024, 35(4): 108901-. doi: 10.1016/j.cclet.2023.108901
7. [7]
  Xiaofen GUAN , Yating LIU , Jia LI , Yiwen HU , Haiyuan DING , Yuanjing SHI , Zhiqiang WANG , Wenmin WANG . Synthesis, crystal structure, and DNA-binding of binuclear lanthanide complexes based on a multidentate Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2486-2496. doi: 10.11862/CJIC.20240122
8. [8]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
9. [9]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
10. [10]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
11. [11]
  Shasha Ma , Zujin Yang , Jianyong Zhang . Facile Synthesis of FeBTC Metal-Organic Gel and Its Adsorption of Cr₂O₇²⁻: A Physical Chemistry Innovation Experiment. University Chemistry, 2024, 39(8): 314-323. doi: 10.3866/PKU.DXHX202401008
12. [12]
  Yuena Yang , Xufang Hu , Yushan Liu , Yaya Kuang , Jian Ling , Qiue Cao , Chuanhua Zhou . The Realm of Smart Hydrogels. University Chemistry, 2024, 39(5): 172-183. doi: 10.3866/PKU.DXHX202310125
13. [13]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
14. [14]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
15. [15]
  Lubing Qin , Fang Sun , Meiyin Li , Hao Fan , Likai Wang , Qing Tang , Chundong Wang , Zhenghua Tang . 原子精确的(AgPd)₂₇团簇用于硝酸盐电还原制氨：一种配体诱导策略来调控金属核. Acta Physico-Chimica Sinica, 2025, 41(1): 2403008-. doi: 10.3866/PKU.WHXB202403008
16. [16]
  Mengzhen JIANG , Qian WANG , Junfeng BAI . Research progress on low-cost ligand-based metal-organic frameworks for carbon dioxide capture from industrial flue gas. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 1-13. doi: 10.11862/CJIC.20240355
17. [17]
  Fengqiao Bi , Jun Wang , Dongmei Yang . Specialized Experimental Design for Chemistry Majors in the Context of “Dual Carbon”: Taking the Assembly and Performance Evaluation of Zinc-Air Fuel Batteries as an Example. University Chemistry, 2024, 39(4): 198-205. doi: 10.3866/PKU.DXHX202311069
18. [18]
  Linhan Tian , Changsheng Lu . Discussion on Sextuple Bonding in Diatomic Motifs of Chromium Family Elements. University Chemistry, 2024, 39(8): 395-402. doi: 10.3866/PKU.DXHX202401056
19. [19]
  Yanan Jiang , Yuchen Ma . Brief Discussion on the Electronic Exchange Interaction in Quantum Chemistry Computations. University Chemistry, 2025, 40(3): 10-15. doi: 10.12461/PKU.DXHX202402058
20. [20]
  Dong-Bing Cheng , Junxin Duan , Haiyu Gao . Experimental Teaching Design on Chitosan Extraction and Preparation of Antibacterial Gel. University Chemistry, 2024, 39(2): 330-339. doi: 10.3866/PKU.DXHX202308053

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(421)
HTML views(91)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142