Citation: Chen Guanghui, He Yanping, Zhang Lei, Zhang Jian. Syntheses and Structural Studies of a Series of Ti₄(embonate)₆-based Complexes[J]. Acta Chimica Sinica, ;2020, 78(12): 1411-1417. doi: 10.6023/A20070337 shu

Syntheses and Structural Studies of a Series of Ti₄(embonate)₆-based Complexes

Chen Guanghui ^a,b ,
He Yanping ^a,, ,
Zhang Lei ^a ,
Zhang Jian ^a,,

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China

Corresponding author: He Yanping, hyp041@163.com Zhang Jian, zhj@fjirsm.ac.cn
Received Date: 31 July 2020
Available Online: 6 August 2020
Fund Project: Project supported by the National Natural Science Foundation of China (No.21935010)the National Natural Science Foundation of China 21935010

Figures(6)

Metal-organic cages (MOCs) as a new type of molecular containers have attracted great interest because of their special cavities and wide applications in molecule recognition and separation, drug delivery and catalysis, etc. However, in the past decades, most researchers just devote to constructing discrete MOCs with special functions. Since many cage compounds are not soluble and stable in the solvent, the further assembly of cages into advanced materials is relatively less developed. In our previous study, we reported a water-soluble and ultrastable Ti₄L₆ (L=embonate) tetrahedron with coordination assembly function, which has been applied as the starting material to realize coordination assembly with different metal ions through two-step reaction. In this work, by employing the Ti₄L₆ cages to assemble with Mn²⁺, Nd³⁺, Ba²⁺ and Ca²⁺ ions, respectively, a series of Ti₄L₆-based complexes have been synthesized under different solvothermal reaction conditions, namely, (Me₂NH₂)₉(Me₄N)[Mn₃(Ti₄L₆)₂(H₂O)₉(DMF)₆]·Guests (PTC-241, DMF=N, N-dimethylformamide); (Me₂NH₂)₅- [Nd(Ti₄L₆)(H₂O)₂(DMF)₅]·Guests (PTC-242); (Me₂NH₂)₂[Ba₄(Ti₄L₆)(OH)₂(H₂O)₈(TEA)₅]·Guests (PTC-243, TEA=Triethanolamine); (Me₂NH₂)₂[Ca₃(Ti₄L₆)(H₂O)₈(DEA)₂]·Guests (PTC-242, DEA=Diethanolamine); (Me₂NH₂)₂[Ca₃(Ti₄L₆)-(H₂O)₁₅]·Guests (PTC-245). Their structures were characterized by X-ray single crystal diffraction, thermo gravimetric analyzer (TGA), infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). Single-crystal analysis reveals that PTC-241 is a supramolecular homochiral architecture formed by the staggered accumulation of ΔΔΔΔ-[Ti₄L₆] and ΔΔΔΔ-[Ti₄L₆]-Mn₃ cages by weak interactions (such as hydrogen bonding and π-π stacking). PTC-242 is also a supramolecular structure, in which the Ti₄L₆-Nd cages are linked by (Me₂NH₂)⁺ cations and ethanediamine (en) molecules via the weak N-H…O hydrogen bonding force, giving rise to a 3D H-bonding framework with a honeycomb lattice of hexagonal channels along the b axis. PTC-243 is a linear Ti₄L₆-Ba₄ chain structure. Both PTC-242 and PTC-245 are two-dimensional (2D) Ti₄L₆-Ca₃ layers with honeycomb-like structures. In addition, we also investigated the fluorescent properties of PTC-242 and PTC-245 in the solid state, and the results show that both of them display strong emitting bands in the visible region.
- titanium-organic cage,
- stepwise assembly,
- synthesis,
- crystal structure
1. [1]
  Cook, T. R.; Stang, P. J. Chem. Rev. 2015, 115, 7001.
2. [2]
  Castilla, A. M.; Ramsay, W. J.; Nitschke, J. R. Acc. Chem. Res. 2014, 47, 2063.
3. [3]
  Sun, Y. Y.; Zhuo, C.; Wang, F.; Zhang, J. Chin. J. Chem. 2020, 38, 449.
4. [4]
  Liu, J. B.; Li, P.; Yao, Z. J. Chin. J. Org. Chem. 2020, 40, 364(in Chinese).
5. [5]
  Chen, Z.; Liu, J.; Cui, H.; Zhang, L.; Su, C. Acta Chim. Sinica 2019, 77, 242(in Chinese).
6. [6]
  Saha, M. L.; Yan, X.; Stang, P. J. Acc. Chem. Res. 2016, 49, 2527.
7. [7]
  Bloch, W. M.; Abe, Y.; Holstein, J. J.; Wandtke, C. M.; Dittrich, B.; Clever, G. H. J. Am. Chem. Soc. 2016, 138, 13750.
8. [8]
  Cullen, W.; Turega, S.; Hunter, C. A.; Ward, M. D. Chem. Sci. 2015, 6, 625.
9. [9]
  Yoshizawa, M.; Klosterman, J. K.; Fujita, M. Angew. Chem. Int. Ed. 2009, 48, 3418.
10. [10]
  Brown, C. J.; Toste, F. D.; Bergman, R. G.; Raymond, K. N. Chem. Rev. 2015, 115, 3012.
11. [11]
  Sun, W.; Ye, L.; Liu, J.; Zheng, L.; Guo, W.; Han, S.; Shao, C.; Jiang, H. Chin. J. Org. Chem. 2019, 39, 2867(in Chinese).
12. [12]
  Li, Y.; Zhang, W.; Liu, Z.; Xie, Z. Acta Chim. Sinica 2015, 73, 641(in Chinese).
13. [13]
  Lorzing, G. R.; Gosselin, E. J.; Trump, B. A.; York, A. H. P.; Sturluson, A.; Rowland, C. A.; Yap, G. P. A.; Brown, C. M.; Simon, C. M.; Bloch, E. D. J. Am. Chem. Soc. 2019, 141, 12128.
14. [14]
  Niu, Z.; Wang, L.; Fang, S.; Lan, P. C.; Aguila, B.; Perman, J.; Ma, J.-G.; Cheng, P.; Li, X.; Ma, S. Chem. Sci. 2019, 10, 6661.
15. [15]
  Frischmann, P. D.; Kunz, V.; Wurthner, F. Angew. Chem. Int. Ed. 2015, 54, 7285.
16. [16]
  Endo, K.; Ube, H.; Shionoya, M. J. Am. Chem. Soc. 2020, 142, 407.
17. [17]
  Fleming, J. S.; Mann, K. L. V.; Carraz, C.-A.; Psillakis, E.; Jeffery, J. C.; McCleverty, J. A.; Ward, M. D. Angew. Chem. Int. Ed. 1998, 37, 1279.
18. [18]
  Zhu, H.-B.; Wu, Y.-F.; Lou, Y.-B.; Hu, J. Synth. Met. 2014, 190, 34.
19. [19]
  Zarra, S.; Smulders, M. M.; Lefebvre, Q.; Clegg, J. K.; Nitschke, J. R. Angew. Chem. Int. Ed. 2012, 51, 6882.
20. [20]
  Young, M. C.; Holloway, L. R.; Johnson, A. M.; Hooley, R. J. Angew. Chem. Int. Ed. 2014, 53, 9832.
21. [21]
  Wan, S.; Lin, L. R.; Zeng, L.; Lin, Y.; Zhang, H. Chem. Commun. 2014, 50, 15301.
22. [22]
  Wang, J.; He, C.; Wu, P.; Wang, J.; Duan, C. J. Am. Chem. Soc. 2011, 133, 12402.
23. [23]
  Yan, L. L.; Tan, C. H.; Zhang, G. L.; Zhou, L. P.; Bunzli, J. C.; Sun, Q. F. J. Am. Chem. Soc. 2015, 137, 8550.
24. [24]
  Li, K.; Zhang, L. Y.; Yan, C.; Wei, S. C.; Pan, M.; Zhang, L.; Su, C. Y. J. Am. Chem. Soc. 2014, 136, 4456.
25. [25]
  Loffler, S.; Lubben, J.; Krause, L.; Stalke, D.; Dittrich, B.; Clever, G. H. J. Am. Chem. Soc. 2015, 137, 1060.
26. [26]
  Bhat, I. A.; Samanta, D.; Mukherjee, P. S. J. Am. Chem. Soc. 2015, 137, 9497.
27. [27]
  Schweiger, M.; Seidel, S. R.; Arif, A. M.; Stang, P. J. Angew. Chem. Int. Ed. 2001, 40, 3467.
28. [28]
  Yuan, Q.-H.; Wan, L.-J.; Jude, H.; Stang, P. J. J. Am. Chem. Soc. 2005, 127, 16279.
29. [29]
  Brückner, C.; Powers, R. E.; Raymond, K. N. Angew. Chem. Int. Ed. 1998, 37, 1837.
30. [30]
  Davis, A. V.; Raymond, K. N. J. Am. Chem. Soc. 2005, 127, 7912.
31. [31]
  Albrecht, M.; Janser, I.; Burk, S.; Weis, P. Dalton Trans. 2006, 2875.
32. [32]
  Albrecht, M.; Burk, S.; Weis, P. Synthesis 2008, 18, 2963.
33. [33]
  Zhu, B. C.; Fang, W. H.; Wang, J.; Du, Y.; Zhou, T.; Wu, K.; Zhang, L.; Zhang, J. Chem. Eur. J. 2018, 24, 14358.
34. [34]
  Li, J.-R.; Timmons, D. J.; Zhou, H.-C. J. Am. Chem. Soc. 2009, 131, 6368.
35. [35]
  He, Y. P.; Yuan, L. B.; Chen, G. H.; Lin, Q. P.; Wang, F.; Zhang, L.; Zhang, J. J. Am. Chem. Soc. 2017, 139, 16845.
36. [36]
  He, Y. P.; Yuan, L. B.; Chen, G. H.; Zhang, L.; Zhang, J. Isr. J. Chem. 2018, 59, 233.
37. [37]
  Chen, G.-H.; Li, H.-Z.; He, Y.-P.; Zhang, S.-H.; Yi, X.; Liang, F.-P.; Zhang, L.; Zhang, J. Cryst. Growth Des. 2020, 20, 29.
38. [38]
  He, Y. P.; Chen, G. H.; Yuan, L. B.; Zhang, L.; Zhang, J. Inorg. Chem. 2020, 59, 964.
39. [39]
  He, Y.-P.; Yuan, L.-B.; Song, J.-S.; Chen, G.-H.; Lin, Q.; Li, C.; Zhang, L.; Zhang, J. Chem. Mater. 2018, 30, 7769.
40. [40]
  Kong, X.-J.; Ren, Y.-P.; Long, L.-S.; Zheng, Z.-P; Nichol, G.; Huang, R.-B.; Zheng, L.-S. Inorg. Chem. 2008, 47, 2728.
41. [41]
  Poncelet, O.; Hubert-Pfalzgraf, L. G.; Toupet, L.; Daran, J. C. Polyhedron 1991, 10, 2045.
42. [42]
  Taeb, A.; Krischner, H.; Kratky, C. Zeitschrift Für Kristallographie 1986, 177, 263.
1. [1]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
2. [2]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
3. [3]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
4. [4]
  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
5. [5]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
6. [6]
  Yan Liu , Yuexiang Zhu , Luhua Lai . Introduction to Blended and Small-Class Teaching in Structural Chemistry: Exploring the Structure and Properties of Crystals. University Chemistry, 2024, 39(3): 1-4. doi: 10.3866/PKU.DXHX202306084
7. [7]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
8. [8]
  Weina Wang , Fengyi Liu , Wenliang Wang . “Extracting Commonality, Delving into Typicals, Deriving Individuality”: Constructing a Knowledge Graph of Crystal Structures. University Chemistry, 2024, 39(3): 36-42. doi: 10.3866/PKU.DXHX202308029
9. [9]
  Junqiao Zhuo , Xinchen Huang , Qi Wang . Symbol Representation of the Packing-Filling Model of the Crystal Structure and Its Application. University Chemistry, 2024, 39(3): 70-77. doi: 10.3866/PKU.DXHX202311100
10. [10]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
11. [11]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
12. [12]
  Yongzhi LI , Han ZHANG , Gangding WANG , Yanwei SUI , Lei HOU , Yaoyu WANG . A two-dimensional metal-organic framework for the determination of nitrofurantoin and nitrofurazone in aqueous solution. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 245-253. doi: 10.11862/CJIC.20240307
13. [13]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
14. [14]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
15. [15]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
16. [16]
  Jinfeng Chu , Lan Jin , Yu-Fei Song . Exploration and Practice of Flipped Classroom in Inorganic Chemistry Experiment: a Case Study on the Preparation of Inorganic Crystalline Compounds. University Chemistry, 2024, 39(2): 248-254. doi: 10.3866/PKU.DXHX202308016
17. [17]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-. doi: 10.3866/PKU.WHXB202406014
18. [18]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
19. [19]
  Wenjie SHI , Fan LU , Mengwei CHEN , Jin WANG , Yingfeng HAN . Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360
20. [20]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017

Get Citation

PDF

XML

Metrics

PDF Downloads(52)
Abstract views(3410)
HTML views(481)

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

Syntheses and Structural Studies of a Series of Ti4(embonate)6-based Complexes

Metrics

通讯作者: 陈斌, bchen63@163.com

Syntheses and Structural Studies of a Series of Ti₄(embonate)₆-based Complexes