Citation: Ruiyan CHEN, Yanping HE, Jian ZHANG. Synthesis and third-order nonlinear optical property of Ti₄L₆ cage-based metal-organic framework[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(10): 2149-2156. doi: 10.11862/CJIC.20250177 shu

Synthesis and third-order nonlinear optical property of Ti₄L₆ cage-based metal-organic framework

Ruiyan CHEN ^{1, 2, 3} ,
Yanping HE ^1,, ,
Jian ZHANG ^2,,

1.
Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi Minzu University, Nanning 530006, China
2.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
3.
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China

Corresponding author: Yanping HE, hyp041@163.com Jian ZHANG, zhj@fjirsm.ac.cn
Received Date: 29 May 2025
Revised Date: 18 August 2025

Figures(5)

Herein, we report the synthesis and third-order nonlinear optical (NLO) properties of a novel cage-based 2D metal-organic framework constructed from Ti₄L₆ (L^4-=embonate) cage combined with Mg²⁺ and tris[4-(1H-imidazol-1-yl)phenyl]amine (tipa) ligand, whose molecular formula is (Me₂CH₂)₂[Mg₃(Ti₄L₆)(tipa)(H₂O)₁₂] (PTC-378). The Ti₄L₆ tetrahedral cages serve as robust building units, while the Mg²⁺ ions and tipa ligands provide structural stability and tunable optical properties. The resulting PTC-378 film exhibited intriguing third-order NLO property, which was systematically investigated using Z-scan techniques. Our results demonstrate that the synergistic interaction between Ti₄L₆ cages and π-conjugated ligands significantly enhances the NLO performance of the materials.
- titanium-organic cage,
- metal-organic framework,
- crystal structure,
- nonlinear optics
1. [1]
  YANG L, ZHANG P, CUI J, CUI X, XING H. The chemistry of metal-organic frameworks for multicomponent gas separation[J]. Angew. Chem.‒Int. Edit., 2024, 63(46): e202414503 doi: 10.1002/anie.202414503
2. [2]
  ZHAO Y, YAMAUCHI Y. Mesoporous single-crystal metal-organic frameworks[J]. Nat. Chem., 2025, 17(2): 161-162 doi: 10.1038/s41557-024-01727-2
3. [3]
  LI H Y, KONG X J, HAN S D, PANG J, HE T, WANG G M, BU X H. Metalation of metal-organic frameworks: Fundamentals and applications[J]. Chem. Soc. Rev., 2024, 53(11): 5626-5676 doi: 10.1039/D3CS00873H
4. [4]
  DHAKSHINAMOORTHY A, LI Z, YANG S, GARCIA H. Metal-organic framework heterojunctions for photocatalysis[J]. Chem. Soc. Rev., 2024, 53(6): 3002-3035 doi: 10.1039/D3CS00205E
5. [5]
  GAO F, WANG X K, CHEN W M, WANG W J, FAN W D, KANG Z X, WANG R M, GUO H L, YUE Q, YUAN D Q, SUN D F. Metal-organic frameworks for hydrogen isotopes separation[J]. Coord. Chem. Rev., 2024, 518: 216047 doi: 10.1016/j.ccr.2024.216047
6. [6]
  HAMACHI T, INOUE M, FUKI M, HONDA T, YABUKI R, PARMAR B, MIYATA K, ONDA K, ITO T, KURASHIGE Y, KOBORI Y, YANAI N. Light-harvesting spin hyperpolarization of organic radicals in a metal-organic framework[J]. J. Am. Chem. Soc., 2025, 147(5): 4365-4374 doi: 10.1021/jacs.4c14916
7. [7]
  CHENG S Q, LIU Y, SUN Y. Macrocycle-based metal-organic and covalent organic framework membranes[J]. Coord. Chem. Rev., 2025, 534: 216559 doi: 10.1016/j.ccr.2025.216559
8. [8]
  ABÁNADES LÁZARO I, CHEN X, DING M, ESKANDARI A, FAIREN-JIMENEZ D, GIMÉNEZ-MARQUÉS M, GREF R, LIN W, LUO T, FORGAN R S. Metal-organic frameworks for biological applications[J]. Nat. Rev. Methods Primers, 2024, 4(1): 42 doi: 10.1038/s43586-024-00320-8
9. [9]
  PARK S, LEE J, KIM B, JUNG C Y, BAE S E, KANG J, MOON D, PARK J. Radical-driven crystal-amorphous-crystal transition of a metal-organic framework[J]. J. Am. Chem. Soc., 2024, 146(13): 9293-9301 doi: 10.1021/jacs.4c01040
10. [10]
  RAJASREE S S, FRY H C, GOSZTOLA D J, SAHA B, KRISHNAN R, DERIA P. Symmetry-breaking charge transfer in metal-organic frameworks[J]. J. Am. Chem. Soc., 2024, 146(8): 5543-5549 doi: 10.1021/jacs.3c13764
11. [11]
  YUAN S, FENG L, WANG K C, PANG J D, BOSCH M, LOLLAR C, SUN Y J, QIN J S, YANG X Y, ZHANG P, WANG Q, ZOU L F, ZHANG Y M, ZHANG L L, FANG Y, LI J L, ZHOU H C. Stable metal-organic frameworks: Design, synthesis, and applications[J]. Adv. Mater., 2018, 30(37): 1704303 doi: 10.1002/adma.201704303
12. [12]
  THORARINSDOTTIR A E, HARRIS T D. Metal-organic framework magnets[J]. Chem. Rev., 2020, 120(16): 8716-8789 doi: 10.1021/acs.chemrev.9b00666
13. [13]
  WANG W, CHEN Y C, BU X H, FENG P Y. Heterometallic aluminum metal-organic frameworks[J]. J. Am. Chem. Soc., 2025, 147(18): 15146-15156 doi: 10.1021/jacs.4c18251
14. [14]
  HE Y P, YUAN L B, CHEN G H, LIN Q P, WANG F, ZHANG L, ZHANG J. Water-soluble and ultrastable Ti₄L₆ tetrahedron with coordination assembly function[J]. J. Am. Chem. Soc., 2017, 139(46): 16845-16851 doi: 10.1021/jacs.7b09463
15. [15]
  CHEN G H, HE Y P, WANG Z R, LI Q H, MA Z Z, ZHANG J. Tunable third-order nonlinear optical effect via modifying Ti₄(embonate)₆ cage-based ionic pairs[J]. Inorg. Chem. Front., 2022, 9(9): 1984-1991 doi: 10.1039/D2QI00138A
16. [16]
  HE Y P, CHEN G H, YUAN L B, ZHANG L, ZHANG J. Ti₄(embonate)₆ cage-ligand strategy on the construction of metal-organic frameworks with high stability and gas sorption properties[J]. Inorg. Chem., 2020, 59(2): 964-967 doi: 10.1021/acs.inorgchem.9b03075
17. [17]
  CHEN G H, HE Y P, YU Y, LI Q H, ZHANG J. Homochiral design of titanium-organic cage for circularly polarized luminescence-based molecular detection[J]. Sci. China Chem., 2023, 66(9): 2558-2562 doi: 10.1007/s11426-023-1707-4
18. [18]
  TENG Q, XIANG G, CHEN G H, CHEN S M, HE Y P, ZHANG J. Coordination assembly of tetrahedral Zr₄(embonate)₆ cages with Eu³⁺ ions[J]. Inorg. Chem., 2021, 60(23): 18178-18184 doi: 10.1021/acs.inorgchem.1c02817
19. [19]
  MENG X, DING Q R, CHEN S M, HE Y P, ZHANG J. Enantioselective assembly of tetrahedral Zr₄(embonate)₆ cages in zeolitic frameworks for synergetic circularly polarized luminescence[J]. Inorg. Chem. Front., 2024, 11(19): 6486-6492 doi: 10.1039/D4QI01624F
20. [20]
  CHEN R Y, HE Y P, CHEN G H, ZHANG J. Designing cage-supported cluster-organic framework for highly efficient optical limiting[J]. ACS Mater. Lett., 2022, 4(8): 1397-1401 doi: 10.1021/acsmaterialslett.2c00343
21. [21]
  YUAN Y, ZHANG D H, LI Q H, CHEN S M, HE Y P, ZHANG J. Combining Ti₄(embonate)₆ anionic cages and π-conjugated coordination cations for highly effective optical limiting[J]. Chem. Commun., 2024, 60(66): 8748-8751 doi: 10.1039/D4CC02938K
22. [22]
  HE Y P, CHEN G H, LI D J, LI Q H, ZHANG L, ZHANG J. Combining a titanium-organic cage and a hydrogen-bonded organic cage for highly effective third-order nonlinear optics[J]. Angew. Chem.‒Int. Edit., 2021, 60(6): 2920-2923 doi: 10.1002/anie.202013977
23. [23]
  LI Y F, HE, Y P, LI Q H, ZHANG J. Integrated anionic zirconium-organic cage and cationic boron-imidazolate cage for synergetic optical limiting[J]. Angew. Chem.‒Int. Edit., 2024, 63(12): e202318806 doi: 10.1002/anie.202318806
24. [24]
  LI J W, DONG W, LIU Y, LI Y, QIAO L Y, LIU G L, ZHANG H, WANG C, ZHENG H L, ZHAO J Q. Water-stable zero-dimensional hybrid zinc halide modulated by π-π interactions: Efficient blue light emission and third-order nonlinear optical response[J]. Inorg. Chem. Front., 2024, 11(23): 8431-8438 doi: 10.1039/D4QI02194K
25. [25]
  WANG S T, LIU Y J, FENG C C, FANG W H, ZHANG J. The largest aluminum molecular rings: Phenol-thermal synthesis, photoluminescence, and optical limiting[J]. Aggregate, 2023, 4(2): e264 doi: 10.1002/agt2.264
26. [26]
  CHEN S, FANG W H, ZHANG L, ZHANG J. Atomically precise multimetallic semiconductive nanoclusters with optical limiting effects[J]. Angew. Chem.‒Int. Edit., 2018, 57(35): 11252-11256 doi: 10.1002/anie.201804569
27. [27]
  LIU Y J, CUI L M, FANG W H, ZHANG J. Design and synthesis of Al₇Ni₂ heterometallic clusters based on metal substitution and ligands protection strategies[J]. Chin. J. Chem., 2023, 41(5): 521-526 doi: 10.1002/cjoc.202200592
28. [28]
  CHEN Y B, ZHANG C Y, LUO D, CHEN R Q, ZHANG J, CHEN S M, FANG W H. Host-guest chemistry and nonlinear optical behaviors of aluminum molecular rings[J]. Chin. J. Chem., 2024, 42(21): 2581-2588 doi: 10.1002/cjoc.202400423
29. [29]
  FU H R, XU Z X, ZHANG J. Water-stable metal-organic frameworks for fast and high dichromate trapping via single-crystal-to-single-crystal ion exchange[J]. Chem. Mater., 2014, 27(1): 205-210
30. [30]
  WANG S T, QI X, CHEN R Q, FANG W H, ZHANG J. Two solvent-dependent Al₁₆ nanorings: Design, synthesis and nonlinear optical limiting behavior[J]. Inorg. Chem. Front., 2024, 11(2): 462-469 doi: 10.1039/D3QI02008H
31. [31]
  ZHANG J F, XIANG Q, YUAN Z, YANG J Y, SONG Y L, ZHANG C. Two W/S/Cu-cluster-containing metal-organic frameworks fabricated by multidentate organic ligands: New topologies, strong NLO properties, and efficient luminescent detection[J]. Cryst. Growth Des., 2021, 21: 3225-3233 doi: 10.1021/acs.cgd.0c01580
32. [32]
  ZHANG R, WANG B, WANG F, CHEN S M, ZHANG J. Syntheses of ferrocene-functionalized indium-based metal-organic frameworks for third order nonlinear optical application[J]. Inorg. Chem. Front., 2023, 10(1): 201-210 doi: 10.1039/D2QI01949C
33. [33]
  CHEN J Q, ZHANG H X, WANG Z R, HONG Q L, ZHANG J. Ligand evolution on trigonal bipyramidal boron imidazolate cages for enhanced optical limiting[J]. Inorg. Chem. Front., 2023, 10(7): 2136-2144 doi: 10.1039/D2QI02742A
34. [34]
  LI D J, LI Q H, WANG Z R, MA Z Z, GU Z G, ZHANG J. Interpenetrated metal-porphyrinic framework for enhanced nonlinear optical limiting[J]. J. Am. Chem. Soc., 2021, 143(41): 17162-17169 doi: 10.1021/jacs.1c07803
1. [1]
  Yukun CHEN , Kexin FENG , Bolun ZHANG , Wentao SONG , Jianjun ZHANG . Syntheses, crystal structures, and diametrically opposed mechanically-stimulated luminescence response of two Mg(Ⅱ) metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1227-1234. doi: 10.11862/CJIC.20240448
2. [2]
  Huan ZHANG , Jijiang WANG , Guang FAN , Long TANG , Erlin YUE , Chao BAI , Xiao WANG , Yuqi ZHANG . A highly stable cadmium(Ⅱ) metal-organic framework for detecting tetracycline and p-nitrophenol. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 646-654. doi: 10.11862/CJIC.20230291
3. [3]
  Hongzhe GUO , Sen WANG , Lu YANG , Fucheng LIU , Jiongpeng ZHAO , Zhaoquan YAO . Highly selective acetylene capture by a pacs-type metal-organic framework constructed using metal-formate complexes as pore partition units. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2157-2164. doi: 10.11862/CJIC.20250179
4. [4]
  Haoying ZHAI , Lanzong WEN , Wenjie LIAO , Qin LI , Wenjun ZHOU , Kun CAO . Metal-organic framework-derived sulfur-doped iron-cobalt tannate nanorods for efficient oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1037-1048. doi: 10.11862/CJIC.20240320
5. [5]
  Xinnan XIE , Boyu ZHANG , Jianxun YANG , Yi ZHONG , Younis Osama , Jianxiao YANG , Xinchun YANG . Ultrafine platinum clusters achieved by metal-organic framework derived cobalt nanoparticle/porous carbon: Remarkable catalytic performance in dehydrogenation of ammonia borane. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2095-2102. doi: 10.11862/CJIC.20250025
6. [6]
  Shanqing YANG , Lulu WANG , Qiang ZHANG , Jiajia LI , Yilong LI , Tongliang HU . A propane-selective metal-organic framework for inverse selective adsorption propane/propylene separation. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2138-2148. doi: 10.11862/CJIC.20250154
7. [7]
  Jie ZHANG , Xin LIU , Zhixin LI , Yuting PEI , Yuqi YANG , Huimin LI , Zhiqiang LIU . Assembling a luminescence silencing system based on post-synthetic modification strategy: A highly sensitive and selective turn-on metal-organic framework probe for ascorbic acid detection. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 823-833. doi: 10.11862/CJIC.20230310
8. [8]
  Weichen WANG , Chunhua GONG , Junyong ZHANG , Yanfeng BI , Hao XU , Jingli XIE . Construction of two metal-organic frameworks by rigid bis(triazole) and carboxylate mixed-ligands and their catalytic properties for CO₂ cycloaddition reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1377-1386. doi: 10.11862/CJIC.20230415
9. [9]
  Meirong HAN , Xiaoyang WEI , Sisi FENG , Yuting BAI . A zinc-based metal-organic framework for fluorescence detection of trace Cu²⁺. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1603-1614. doi: 10.11862/CJIC.20240150
10. [10]
  Ruikui YAN , Xiaoli CHEN , Miao CAI , Jing REN , Huali CUI , Hua YANG , Jijiang WANG . Design, synthesis, and fluorescence sensing performance of highly sensitive and multi-response lanthanide metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 834-848. doi: 10.11862/CJIC.20230301
11. [11]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
12. [12]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359
13. [13]
  Jia JI , Zhaoyang GUO , Wenni LEI , Jiawei ZHENG , Haorong QIN , Jiahong YAN , Yinling HOU , Xiaoyan XIN , Wenmin WANG . Two dinuclear Gd(Ⅲ)-based complexes constructed by a multidentate diacylhydrazone ligand: Crystal structure, magnetocaloric effect, and biological activity. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 761-772. doi: 10.11862/CJIC.20240344
14. [14]
  Yingyue ZHANG , Liuqing KANG , Yating YANG , Xiaofen GUAN , Wenmin WANG . Crystal structure and antibacterial activity of two Gd₂ complexes based on polydentate Schiff-base ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1867-1877. doi: 10.11862/CJIC.20250100
15. [15]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
16. [16]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
17. [17]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
18. [18]
  Xiumei LI , Linlin LI , Bo LIU , Yaru PAN . Syntheses, crystal structures, and characterizations of two cadmium(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 613-623. doi: 10.11862/CJIC.20240273
19. [19]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
20. [20]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(27)
HTML views(5)

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

Synthesis and third-order nonlinear optical property of Ti4L6 cage-based metal-organic framework

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis and third-order nonlinear optical property of Ti₄L₆ cage-based metal-organic framework