Citation: Liyang ZHANG, Dongdong YANG, Ning LI, Yuanyu YANG, Qi MA. Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079 shu

Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate

School of Chemistry and Environmental Engineering, Shanxi Datong University, Datong, Shanxi 037009, China

Corresponding author: Qi MA, maqihx@163.com
Received Date: 13 March 2024
Revised Date: 30 August 2024

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We have successfully synthesized three cadmium(Ⅱ) complexes [Cd(Hppb)₂Br₂] (1), [Cd₂(ppb)₂Br₂] (2) and [Cd(Hppb)Br₂]_n (3) in which the bromide ions are involved based on an asymmetric ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate (Hppb). Employment of different synthetic conditions has resulted in different architectures. In the three complexes, the ratios of Cd(Ⅱ) ions, ligands, and bromide ions were 1∶2∶2, 1∶1∶1, and 1∶1∶2, respectively, resulting in different structures of mononuclear (0D), binuclear (0D), and 1D framework. The Cd(Ⅱ) coordinated environments in 1 are slightly distorted octahedral geometries, but central ions in 2 and 3 display distorted square pyramidal geometries. There are obvious differences in the ligation modes of the ppb^- or Hppb ligands for both complexes. In 1, two Hppb ligands display μ₁-κN, N′ coordination modes. In 2, two ppb^- ligands display μ₂-κN, N′∶κO coordination modes. Two ppb^- ligands act as two μ_{1, 1}-bridges linking the binuclear Cd(Ⅱ) cations with a distance of 0.409 1(4) nm. In 3, the neutral Hppb ligands exhibit a μ₂-κN, N′∶κO coordination mode, and connecting Cd(Ⅱ) ions by μ_{1, 6}-bridges and forming an infinite 1D chain along the b-axis. The complexes were both studied using Hirshfeld surface analyses and 2D fingerprint plots. Moreover, the photoluminescent properties of 1-3 indicate that the coordination anions make a great contribution to the fluorescent emission of Cd(Ⅱ) polymers.
- 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate,
- cadmium(Ⅱ) complex,
- luminescent property
1. [1]
  Dey C, Kundu T, Biswal B P, Mallick A, Banerjee R. Crystalline metal-organic frameworks (MOFs): Synthesis, structure and function. Acta Crystallogr. Sect. B, 2014, 70(S1): 3-10
2. [2]
  Stock N, Biswas S. Synthesis of metal-organic frameworks (MOFs): Routes to various mof topologies, morphologies, and composites. Chem. Rev., 2011, 112(2): 933-969
3. [3]
  Ren J, Dyosiba X, Musyoka N M, Langmi H W, Mathe M, Liao S. Review on the current practices and efforts towards pilot-scale production of metal-organic frameworks (MOFs). Coord. Chem. Rev., 2017, 352: 187-219 doi: 10.1016/j.ccr.2017.09.005
4. [4]
  Yang L, Liu Y L, Liu C G, Ye F, Fu Y. A luminescent sensor based on a new Cd-MOF for nitro explosives and organophosphorus pesticides detection. Inorg. Chem. Commun., 2020, 122: 108272 doi: 10.1016/j.inoche.2020.108272
5. [5]
  Dong J, Zhao D, Lu Y, Sun W Y. Photoluminescent metal-organic frameworks and their application for sensing biomolecules. J. Mater. Chem. A, 2019, 7(40): 22744-22767 doi: 10.1039/C9TA07022B
6. [6]
  Ma W P, Yan B. Lanthanide functionalized MOF thin films as effective luminescent materials and chemical sensors for ammonia. Dalton Trans., 2020, 49(44): 15663-15671 doi: 10.1039/D0DT03069D
7. [7]
  Zahedi M, Shaabani B, Englert U, Rad-yousefnia N, Blake G R, Kazak C. Cd(Ⅱ) coordination polymers based on expanded N, N′-heteroaromatic donor ligands. Polyhedron, 2017, 133: 110-118 doi: 10.1016/j.poly.2017.05.023
8. [8]
  Zhang Y J, Gao L L, Ma S, Hu T P. Porous MB@Cd-MOF obtained by post-modification: Self-calibrated fluorescent turn-on sensor for highly sensitive detection of carbaryl. Cryst. Growth Des., 2022, 22(4): 2662-2669 doi: 10.1021/acs.cgd.2c00089
9. [9]
  Jin S W, Lin Z H, Zhou Y, Wang D Q, Chen G Q, Ji Z Y, Huang T S. Syntheses, characterization and crystal structures of eight Cd(Ⅱ) carboxylates containing 3,5-dimethylpyrazole. Polyhedron, 2014, 74: 79-92 doi: 10.1016/j.poly.2014.02.041
10. [10]
  Nath B, Baruah J B. Cadmium(Ⅱ) dicarboxylate complexes of 2,2′-[2-fluoro-phenylmethylidenebis (3,5-methyl-2-phenyleneoxy)]diacetic acid formed in different solvents. Polyhedron, 2014, 79: 291-299 doi: 10.1016/j.poly.2014.04.057
11. [11]
  Deka R, Rajak R, Kumar V, Mobin S M. Effect of electrolytic cations on a 3D Cd-MOF for supercapacitive electrodes. Inorg. Chem., 2023, 62(7): 3084-3094 doi: 10.1021/acs.inorgchem.2c03879
12. [12]
  Zikode M, Ojwach S O, Akerman M P. Structurally rigid bis(pyrazolyl)pyridine Zn(Ⅱ) and Cu(Ⅱ) complexes: Structures and kinetic studies in ring-opening polymerization of ε-caprolactone. Appl. Organomet. Chem., 2016, 31(2): e3556
13. [13]
  Zhang L Y, Lu LP, Zhu M L. Two cadmium(Ⅱ) complexes constructed by 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate: Crystal structures, luminescent properties and Hirshfeld surface analyses. J. Chem. Crystallogr., 2019, 50(2): 122-132
14. [14]
  Xu L, Yan S, Choi E Y, Lee J Y, Kwon Y U. Product control by halide ions of ionic liquids in the ionothermal syntheses of Ni-(H)BTC metal-organic frameworks. Chem. Commun., 2009(23): 3431-3433 doi: 10.1039/b902223f
15. [15]
  Bai H Y, Ma J F, Yang J, Liu Y Y, Hua W, Ma J C. Effect of anions on the self-assembly of Cd(Ⅱ)-containing coordination polymers based on a novel flexible tetrakis(imidazole) ligand. Cryst. Growth. Des., 2009, 10(2): 995-1016
16. [16]
  Saxena P, Thirupathi N. Reactions of Cd(OAc)₂·2H₂O with variously substituted pyridines: Efforts to unravel the factors that determine structure/nuclearity of the products. Polyhedron, 2015, 98: 238-250 doi: 10.1016/j.poly.2015.06.002
17. [17]
  Zahedi M, Shaabani B, Englert U, van Leusen J. Organic-inorganic hybrid materials from divalent metal cations and expanded N, N′-donor linkers. Z. Krist.-Cryst. Mater., 2018, 233(2): 97-111 doi: 10.1515/zkri-2017-2084
18. [18]
  Mandal A, Patel B K. Molecular structures and fluorescence property of Zn(Ⅱ), Cd(Ⅱ) complexes of 3-pyridyl-5-aryl-(1H)-1,2,4-triazoles. Polyhedron, 2017, 132: 112-122 doi: 10.1016/j.poly.2017.04.040
19. [19]
  Menzel S, Millan S, Hofert S P, Nuhnen A, Gokpinar S, Schmitz A, Janiak C. Increase of network hydrophilicity from sql to lvt supramolecular isomers of Cu-MOFs with the bifunctional 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate linker. Dalton Trans., 2020, 49(36): 12854-12864 doi: 10.1039/D0DT02642E
20. [20]
  Jin S W, Liu H, Chen G Q, An Z Y, Lou Y L, Huang K, Wang D Q. Syntheses and crystal structures of copper(Ⅱ), zinc(Ⅱ) and cadmium(Ⅱ) complexes containing pyridine, quinoline and 2-methylquinoline. Polyhedron, 2015, 95: 91-107 doi: 10.1016/j.poly.2015.04.017
21. [21]
  Sheldrick G M. SHELXT: Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A, 2015, A71: 3-8
22. [22]
  Spackman M A, McKinnon J J, Jayatilaka D. Electrostatic potentials mapped on Hirshfeld surfaces provide direct insight into intermolecular interactions in crystals. CrystEngComm, 2008, 10(4): 377-388
23. [23]
  Spackman M A, McKinnon J J. Fingerprinting intermolecular interactions in molecular crystals. CrystEngComm, 2002, 4(66): 378-392 doi: 10.1039/B203191B
24. [24]
  McKinnon J J, Mitchell A S, Spackman MA. Hirshfeld surfaces: A new tool for visualising and exploring molecular crystals. Chem.-Eur. J., 1998, 4(11): 2136-2141 doi: 10.1002/(SICI)1521-3765(19981102)4:11<2136::AID-CHEM2136>3.0.CO;2-G
25. [25]
  Yang D D, Lu L P, Zhu M L. A design for detecting phosphate ions in aqueous solution by luminescent Tb-coordination polymer. Inorg. Chimi. Acta, 2021, 515: 120030 doi: 10.1016/j.ica.2020.120030
26. [26]
  Yang D D, Liu X X, Lu L, Zhu M L. Effects of two different solvents on the syntheses, structural diversity, and magnetic properties of six Mn(Ⅱ) complexes derived from 3,3′-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoate and variable N-donor ligands. CrystEngComm, 2020, 22(46): 8088-8099 doi: 10.1039/D0CE01383H
27. [27]
  Yang F, Ren Y X, Li D S, Fu F, Qi G C, Wang Y Y. 1D zigzag chain and 0D monomer Cd(Ⅱ)/Zn(Ⅱ) compounds based on flexible phenylenediacetic ligand: Synthesis, crystal structures and fluorescent properties. J. Mol. Struct., 2008, 892(1/2/3): 283-288
28. [28]
  Addison A W, Rao T N, Reedijk J, Vanrijn J, Verschoor G C. Synthesis, structure, and spectroscopic properties of copper(Ⅱ) compounds containing nitrogen sulfur donor ligands: The crystal and molecular-structure of aqua[1,7-bis(n-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(Ⅱ) perchlorate. J. Chem. Soc. Dalton Trans., 1984(7): 1349-1356 doi: 10.1039/DT9840001349
29. [29]
  Zheng S L, Yang J H, Yu X L, Chen X M, Wong W T. Syntheses, structures, photoluminescence, and theoretical studies of d¹⁰ metal complexes of 2,2′-dihydroxy-[1, 1′]binaphthalenyl-3,3′-dicarboxylate. Inorg. Chem., 2004, 43: 830-838 doi: 10.1021/ic034847i
30. [30]
  LI J K, ZHAO S H, HU C W. Polyoxometalate-based host-guest framework materials POMs@MOFs(COFs). Chinese J. Inorg. Chem., 2019, 35(11): 1934-1956 doi: 10.11862/CJIC.2019.230
31. [31]
  LI F F, HE J. Synthesis, structural and magnetic characterization of Fe(Ⅱ)/Co(Ⅱ)isomorphous complexes based on a dipyrazole-containing tetracarboxylate ligand. Chinese J. Inorg. Chem., 2022, 38(11): 2259-2266 doi: 10.11862/CJIC.2022.226
32. [32]
  WANG G F, SUN X W, SONG S F, LÜ M. Synthesis of a Cd(Ⅱ)-based coordination polymer for luminescence detecting 2,4,6-trinitrophenol. Chinese J. Inorg. Chem., 2023, 39(12): 2407-2414 doi: 10.11862/CJIC.2023.197
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