Citation: Kaimin WANG, Na HE, Shiyi LI, Xuling BAI, Weiqing SUN, Yanqing YE, Yulu MA. Synthesis, Hirshfeld surface analysis and properties of two Zn(Ⅱ)/Ni(Ⅱ) coordination polymers[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(1): 55-64. doi: 10.11862/CJIC.20250178 shu

Synthesis, Hirshfeld surface analysis and properties of two Zn(Ⅱ)/Ni(Ⅱ) coordination polymers

Kaimin WANG ¹ ,
Na HE ¹ ,
Shiyi LI ¹ ,
Xuling BAI ¹ ,
Weiqing SUN ¹ ,
Yanqing YE ¹ ,
Yulu MA ^{2, 3,,}

1.
School of Chemistry & Environment, Yunnan Minzu University, Kunming 650504, China
2.
School of Pharmaceutical Sciences, Yunnan Key Laboratory of Pharmacology for Natural Products, Kunming Medical University, Kunming 650500, China
3.
College of Modern Biomedical Industry, Kunming Medical University, Kunming 650500, China

Corresponding author: Yulu MA, yuluma163@163.com
Received Date: 29 May 2025
Revised Date: 22 September 2025

Figures(9)

Two coordination polymers with different properties were successfully constructed under solvothermal conditions using zinc perchlorate, nickel perchlorate, and the same mixed ligand composed of 2, 7-naphthalenedicarboxylic acid (H₂NDA) and 1, 4-bis(1H-imidazol-1-yl)benzene (1, 4-DMB): {[Zn(NDA)(1, 4-DMB)_0.5(H₂O)]}_n (Zn-CP) and {[Ni(NDA)(1, 4-DMB)(H₂O)₃]}_n (Ni-CP). Single-crystal X-ray diffraction, thermogravimetric analysis, Hirshfeld surface analysis, and other characterization methods further explored the phase purity, thermal stability, and interaction in the crystal of the two complexes. The results show that the two coordination polymers have a 1D chain structure, and both of them are finally separated by abundant intermolecular hydrogen bonds and π…π stacking interactions form a 3D supramolecular structure. However, it is worth noting that when the two complexes are synthesized, except for the metal cations, the anions and other reagents and conditions are the same. Still, in Zn-CP, Zn²⁺ is in the center of the deformed tetrahedron with four coordinations, and the carboxyl groups in the NDA^2- ligands are all involved in the coordination, which is a bidentate bridging ligand. The final structure of the coordination polymer is a 1D ladder-shaped chain. In Ni-CP, Ni²⁺ is in the center of the deformed octahedron with hexacoordination, but only one carboxyl group is involved in the coordination in the NDA^2- ligand, which is a monodentate ligand end-group ligand, so the coordination polymer is only a 1D twisted trapezoidal chain. In addition, the solid-state fluorescence test results under 275 nm excitation showed that Zn-CP exhibited good fluorescence properties at 363 nm. Furthermore, the electrocatalytic performance test for nitrate reduction to ammonia indicated that Ni-CP exhibited a certain degree of electrocatalytic ability for nitrate reduction to ammonia.
- coordination polymers,
- Hirshfeld surface analysis,
- fluorescence properties,
- electrocatalysis,
- nitrate reduction
1. [1]
  OSYPIUK D, BARTYZEL A, CRISTÓVÃO B. Coordination polymers of vanadium and selected metal ions with N, O-donor schiff base ligands-synthesis, crystal structure, and application[J]. Molecules, 2025, 30(5): 1104 doi: 10.3390/molecules30051104
2. [2]
  WANG K M, ZHAO X, BAI X L, DONG Y Q, FAN R F, YU H M, TANG H J, MA Y L. A fluorescence sensor based on Cd(Ⅱ) coordination polymer for recognition of nitrofurantoin[J]. Chinese J. Inorg. Chem., 2023, 39(8): 1587-1596 doi: 10.11862/CJIC.2023.125
3. [3]
  OMOTO K, RAPENNE G. Design of crystalline layered coordination polymers that respond to light and heat stimuli[J]. Dalton Trans., 2025, 54: 7179-7188 doi: 10.1039/D5DT00156K
4. [4]
  KUMAR S, MUHAMMAD R, AMHAMED A, OH H. Unveiling the potential of ingenious copper-based metal-organic frameworks in gas storage and separation[J]. Coord. Chem. Rev., 2025, 522: 216230 doi: 10.1016/j.ccr.2024.216230
5. [5]
  JIANG R Y, ZHENG S T, ZHANG L P, PEI L M, WANG J, LEI Z, ZHENG F, WANG W B, JIANG Y, WANG S M, YANG Q Y. Nanoporous copper-isoquinoline coordination polymer for high-efficiency ethane/ethylene separation[J]. ACS Appl. Nano Mater., 2025, 8(19): 10080-10086 doi: 10.1021/acsanm.5c01531
6. [6]
  LIU Z N, XING C Y, SHAN Y F, MA M, WU S W, GE R X, XUE Q Z, TIAN J. Molecular engineering of 1D conjugated copper anilate coordination polymers for boosting electrocatalytic nitrate reduction to ammonia[J]. Chem. Sci., 2025, 16(16): 7010-7017 doi: 10.1039/D4SC08508F
7. [7]
  MA Y L, YANG L P, BAI X L, WANG K M. Sensitive detection of organophosphorus pesticides in agricultural food products by a highly luminescent coordination polymer[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 2025, 341: 126471 doi: 10.1016/j.saa.2025.126471
8. [8]
  CHI Z M, CHU S Q, WANG B Q, ZHANG Z, LIU G H, WANG X L. Advances in metal complex-based colorimetric sensors[J]. Talanta, 2026, 297: 128591 doi: 10.1016/j.talanta.2025.128591
9. [9]
  ZHONG B Q, LIU J L, LIU G C, ZHANG Z, CHEN Y Q, WANG X L. pH-directed polyoxometalate-based supramolecular framework for effectively electrochemical sensing IO₃^- from glycerol oxidation wastewater[J]. J. Mol. Struct., 2025, 1332: 141679
10. [10]
  WU R, CHEN Y H, YU H J, XU H L, ZHONG S L. Coordination polymer nanospheres based on folic acid: Upconversion properties, cytotoxicity study and drug delivery[J]. Mater. Lett., 2023, 335: 133785 doi: 10.1016/j.matlet.2022.133785
11. [11]
  LUO Y H, XUE C, ZHANG S X, ZHAO J, JIN X T, LIU M. Charge transfer-triggered reversible spin-state switching [J]. J. Mater. Chem. C, 2024, 12: 1693-1700 doi: 10.1039/D3TC03907B
12. [12]
  LIU M, MA S H, DONG H, ZENG F L, JIN X T, LUO Y H. Rewritable paper based on layered metal-organic frameworks with NIR-triggered reversible color switching[J]. Adv. Opt. Mater., 2023, 11: 2300056 doi: 10.1002/adom.202300056
13. [13]
  LIU M, LIU Q, JIN X T, ZOU Y C, LI D N, FENG P, LUO Y H. Removal of total chromium in wastewater via simultaneous photocatalysis and adsorption using calcium silicate hydrate-based composites[J]. J. Mater. Chem. A, 2023, 11: 24038-24046 doi: 10.1039/D3TA05384A
14. [14]
  PAVLOV D I, RYADUN A A, FEDIN V P, POTAPOV A S. Zinc metal-organic coordination polymer with 4, 7-di(1, 2, 4-triazol-1-yl)-2, 1, 3-benzothiadiazole and 1, 4-naphthalene dicarboxylic acid: Luminescent properties and guest-host charge transfer[J]. J. Struct. Chem., 2024, 65: 2567-2578 doi: 10.1134/S0022476624120199
15. [15]
  FU Y Y, CHEN J L, YANG F Y, LI J F, LIU Q Y, WANG J W, LIU J J. Two one-dimensional functional coordination polymers based on 1, 1′-bis(3-carboxybenzyl)-4, 4′-bipyridinium moiety[J]. Polyhedron, 2024, 255: 116983 doi: 10.1016/j.poly.2024.116983
16. [16]
  CHEN Z L, YANG J, CHENG W W, HUANG J, YANG D, XUE Y S, WU X H. A novel coordination polymer based on 2, 6-naphthalenedicarboxylic acid: Synthesis, crystal structure and luminescence sensing[J]. Transit. Met. Chem., 2020, 45: 121-128 doi: 10.1007/s11243-019-00364-w
17. [17]
  WEN M Y, FU L S, DONG G Y. Two Cd(Ⅱ)-based metal-organic frameworks as difunctional fluorescence sensors to detect enrofloxacin and Fe³⁺[J]. J. Solid State Chem., 2022, 315: 123483 doi: 10.1016/j.jssc.2022.123483
18. [18]
  DENG N, CHEN L, BAI X L, WANG K M, HE N, YE Y Q, MA Y L. Synthesis, crystal structure and adsorption properties of a novel Co(Ⅱ) coordination polymer[J]. Inorg. Chem. Commun., 2025, 180: 115059 doi: 10.1016/j.inoche.2025.115059
19. [19]
  SI G R, KONG X J, HE T, ZHAO J T, XIE L H, LI J R. Ammonia hydration in a Cu(Ⅱ)-pyrazolate framework for efficient trace capture[J]. Angew. Chem. ‒Int. Edit., 2025: e202507356
20. [20]
  YANG Y, SUN Y T, WANG Y N, ZHANG X X, ZHANG W Y, HUANG Z F, YIN L C, HAN A L, LIU G. Self-triggering a locally alkaline microenvironment of Co₄Fe₆ for highly efficient neutral ammonia electrosynthesis[J]. J. Am. Chem. Soc., 2025, 147(10): 8893-8905 doi: 10.1021/jacs.5c00688
21. [21]
  WANG M, MENG Y R, XU W J, SHEN T Y, WANG Y H, YU Q C, LIU C J, GU Y M, TIE Z X, FAN Z X, ZUO J L, SU J, JIN Z. Square-planar tetranuclear cluster-based high-symmetry coordination metal-organic polymers for efficient electrochemical nitrate reduction to ammonia[J]. J. Am. Chem. Soc., 2025, 147(21): 18327-18337 doi: 10.1021/jacs.5c06650
22. [22]
  SHELDRICK G M. Crystal structure refinement with SHELXL[J]. Acta Crystallogr. Sect. C, 2015, C71(1): 3-8
23. [23]
  DOLOMANOV O V, BOURHIS L J, GILDER R J, HOWARDA J A K, PUSCHMANNA H. OLEX2: A complete structure solution, refinement and analysis program[J]. J. Appl. Crystallogr., 2009, 42: 339-341 doi: 10.1107/S0021889808042726
24. [24]
  CUI P P, LI X, CHEN Y L, CHENG Z L, GAO F Y, GUO X, YAN W N, DENG Y C. Transition metal coordination polymers with flexible dicarboxylate ligand: Synthesis, characterization, and photoluminescence property[J]. Chinese J. Inorg. Chem., 2024, 40(11): 2221-2231 doi: 10.11862/CJIC.20240234
25. [25]
  WANG J F, XU X, BIAN R N, DONG W K, DING Y J. Investigation on structurally different Cu(Ⅱ) and Ni(Ⅱ) complexes constructed from a novel pyridine-terminal salamo-like ligand[J]. Inorg. Chim. Acta, 2021, 516: 120095 doi: 10.1016/j.ica.2020.120095
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