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Luminescent lanthanide metallogels: situ fabrication, self-healing and rheological properties

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Abstract

We have presented a simple method for situ fabrication of photoluminescent lanthanide metallogels. A series of lanthanide metallogels could be rapidly formed through mixing the aqueous solution of Tb3+ or Eu3+ and organic solution of synthesized aromatic carboxylic ligands (DCn, n = 14, 16,18) at room temperature. The gelation tests revealed that the ligand with longer alkyl chain (DC18) showed stronger gelling abilities, indicating that the structure of non-coordinated groups in ligand molecules could affect self-assembly processes and, hence, the microstructures and properties of lanthanide metallogels. FT-IR measurements demonstrated that the driving force of formation of the metallogels was the coordination interaction between DCn and Tb3+ or Eu3+. XRD analysis revealed that DC14 metallogels took a mixture of hexagonal and tetragonal packing modes. All obtained metallogels have shown typical luminescent emissions of the lanthanide complex. In particular, DC18/Tb(NO3)3 metallogel in DMF/H2O (v:v = 1:1) has shown excellent self-supporting, self-healing, film-forming, and rheological properties.

The Tb3+/Eu3+ metallogels have been formed with aromatic carboxylic acids as ligands, and they have shown excellent luminescent, self-healing, film-forming, and rheological properties.

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References

  1. Whitesides GM, Grzybowski BA (2005) Self-assembly at all scales. Science 295(29):2418–2421

    Google Scholar 

  2. Jones CD, Steed JW (2016) Gels with sense: supramolecular materials that respond to heat, light and sound. Chem Soc Rev 45(23):6546–6596

    CAS  PubMed  Google Scholar 

  3. Kishimura A, Yamashita T, Aida T (2005) Phosphorescent organogels via “metallophilic” interactions for reversible RGB-color switching. J Am Chem Soc 127(1):179–183

    CAS  PubMed  Google Scholar 

  4. Dong S, Luo Y, Yan X, Zheng B, Ding X, Yu Y, Ma Z, Zhao Q, Huang F (2011) A dual-responsive supramolecular polymer gel formed by crown ether based molecular recognition. Angew Chem Int Ed Engl 50(8):1905–1909

    CAS  PubMed  Google Scholar 

  5. Rodriguez F, Miravet JF, Escuder B (2009) A supramolecular hydrogel as a reusable heterogeneous catalyst for the direct aldol reaction. Chem Commun 47:7303–7305

    Google Scholar 

  6. Kawano SI, Tamaru SI, Fujita N, Shinkai S (2004) Sol-gel polycondensation of tetraethyl orthosilicate (TEOS) in sugar-based porphyrin organogels: inorganic conversion of a sugar-directed porphyrinic fiver library through sol-gel transcription processes. Chem Eur J 10(2):343–351

    CAS  PubMed  Google Scholar 

  7. Okesola BO, Smith DK (2016) Applying low-molecular weight supramolecular gelators in an environmental setting - self-assembled gels as smart materials for pollutant removal. Chem Soc Rev 45(15):4226–4251

    CAS  PubMed  Google Scholar 

  8. Xu ZY, Peng JX, Yan N, Yu H, Zhang SS, Liu KQ, Fang Y (2013) Simple design but marvelous performances: molecular gels of superior strength and self-healing properties. Soft Matter 9(4):1091–1099

    CAS  Google Scholar 

  9. Piepenbrock MM, Lloyd GO, Clarke N, Steed JW (2010) Metal- and anion-binding supramolecular gels. Chem Rev 110(4):1960–2004

    CAS  PubMed  Google Scholar 

  10. Tam AYY, Yam VWW (2013) Recent advances in metallogels. Chem Soc Rev 42(4):1540–1567

    CAS  PubMed  Google Scholar 

  11. Zhang J, Su CY (2013) Metal-organic gels: from discrete metallogelators to coordination polymers. Coord Chem Rev 257(7–8):1373–1408

    CAS  Google Scholar 

  12. Sutar P, Maji TK (2016) Coordination polymer gels: soft metal-organic supramolecular materials and versatile applications. Chem Commun 52(52):8055–8074

    CAS  Google Scholar 

  13. Häring M, Díaz DD (2016) Supramolecular metallogels with bulk self-healing properties prepared by in situ metal complexation. Chem Commun 52(89):13068–13081

    Google Scholar 

  14. Karak S, Kumar S, Bera S, Díaz Díaz D, Banerjee S, Vanka K, Banerjee R (2017) Interplaying anions in a supramolecular metallohydrogel to form metal organic framework. Chem Commun 53(26):3705–3708

    CAS  Google Scholar 

  15. Ganta S, Chand DK (2018) Multi-stimuli-responsive metallogel molded from a Pd2L4-type coordination cage: selective removal of anionic dyes. Inorg Chem 57(7):3634–3645

    CAS  PubMed  Google Scholar 

  16. Xue M, Lü YC, Sun QQ, Liu KQ, Liu Z, Sun P (2015) Ag(I)-coordinated supramolecular metallogels based on Schiff base ligands: structural characterization and reversible thixotropic property. Cryst Growth Des 15(11):5360–5367

    CAS  Google Scholar 

  17. Park J, Lee JH, Jawprski J, Shinkai S, Jung JH (2014) Luminescent calyx[4]arene-based metallogel formed at different solvent composition. Inorg Chem 53(14):7181–7187

    CAS  PubMed  Google Scholar 

  18. Karan CK, Sau MC, Bhattacharjee M (2017) A copper(II) metal-organic hydrogel as a multifunctional precatalyst for CuAAC reactions and chemical fixation of CO2 under solvent free conditions. Chem Commun 53(9):1526–1529

    CAS  Google Scholar 

  19. Mitsumoto K, Cameron JM, Wei RJ, Nishikawa H, Shiga T, Nihei M, Newton GN, Oshio H (2017) A multi-redox responsive cyanometalate-based metallogel. Chem Eur J 23(7):1502–1506

    CAS  PubMed  Google Scholar 

  20. Lin Q, Lu TT, Zhu X, Sun B, Yang QP, Wei TB, Zhang YM (2015) A novel supramolecular metallogel-based high-resolution anion sensor array. Chem Commun 51(9):1635–1638

    CAS  Google Scholar 

  21. Mallick A, Schön E, Panda T, Sreenivas K, Díaz D, Banerjee R (2012) Fine-tuning the balance between crystallization and gelation and enhancement of CO2 uptake on functionalized calcium based MOFs and metallogels. J Mater Chem 22(30):14951–14963

    CAS  Google Scholar 

  22. Qin X, Liu XW, Huang W, Bettinelli M, Liu XG (2017) Lanthanide-activated phosphors based on 4f-5d optical transitions: theoretical and experimental aspects. Chem Rev 117(5):4488–4527

    CAS  PubMed  Google Scholar 

  23. Eliseeva SV, Bünzli JG (2010) Lanthanide luminescence for functional materials and bio-sciences. Chem Soc Rev 39(1):189–227

    CAS  PubMed  Google Scholar 

  24. Feng J, Zhang HJ (2013) Hybrid materials based on lanthanide organic complexes: a review. Chem Soc Rev 42(1):387–410

    CAS  PubMed  Google Scholar 

  25. Binnemans K (2009) Lanthanide-based luminescent hybrid materials. Chem Rev 109(9):4283–4374

    CAS  PubMed  Google Scholar 

  26. dos Santos CMG, Harte AJ, Quinn SJ, Gunnlaugsson T (2008) Recent developments in the field of supramolecular lanthanide luminescent sensors and self-assemblies. Coord Chem Rev 252(23–24):2512–2572

    Google Scholar 

  27. Rajendran M, Yapici E, Miller LW (2014) Lanthanide-based imaging of protein interactions in live cells. Inorg Chem 53(4):1839–1853

    CAS  PubMed  Google Scholar 

  28. Shavaleev NM, Eliseeva SV, Scopelliti R, Bünzli JG (2015) Influence of symmetry on the luminescence and radiative lifetime of nine-coordinate europium complexes. Inorg Chem 54(18):9166–9173

    CAS  PubMed  Google Scholar 

  29. Kotova O, Daly R, dos Santosv CMG, Boese M, Kruger PE, Boland JJ, Gunnlaugsson T (2012) Europium-directed self-assembly of a luminescent supramolecular gel from a tripodal terpyridine-based ligand. Angew Chem Int Ed 51(1):1–6

    Google Scholar 

  30. Martínez-Calvo M, Kotova O, Möbius ME, Bell AP, McCabe T, Boland JJ, Gunnlaugsson T (2015) Healable luminescent self-assembly supramolecular metallogels possessing lanthanide (Eu/Tb) dependent rheological and morphological properties. J Am Chem Soc 137(5):1983–1992

    PubMed  Google Scholar 

  31. Chen PK, Li QC, Grindy S, Holten-Andersen N (2015) White-light-emitting lanthanide metallogels with tunable luminescence and reversible stimuli-responsive properties. J Am Chem Soc 137(36):11590–11593

    CAS  PubMed  Google Scholar 

  32. Ma XX, Cui YQ, Liu SW, Wu JC (2017) A thermo-responsive supramolecular gel and its luminescence enhancement induced by rare earth Y3+. Soft Matter 13(44):8027–8030

    CAS  PubMed  Google Scholar 

  33. Pedireddi VR, Varughese S (2004) Solvent-dependent coordination polymers: cobalt complexes of 3,5-dinitrobenzoic acid and 3,5-dinitro-4-methylbenzoic acid with 4,4′-bipyrdine. Inorg Chem 43(2):450–457

    CAS  PubMed  Google Scholar 

  34. Carlucci L, Ciani G, Proserpio DM, Sironi A (1995) Novel networks of unusually coordinated silver (I) cations: the wafer-like structure of [Ag(pyz)2][Ag2(pyz)5](PF6)3•2G and the simple cubic frame of [Ag(pyz)3](SbF6). Angew Chem Int Ed Engl 34(17):1895–1898

    CAS  Google Scholar 

  35. Ma XX, Yu DW, Tang N, Wu JC (2014) Tb3+-containing supramolecular hydrogels: luminescence properties and reversible sol-gel transitions induced by external stimuli. Dalton Trans 43(26):9856–9859

    CAS  PubMed  Google Scholar 

  36. Hu JS, Guo YG, Liang HP, Wan LJ, Jiang L (2005) Three-dimensional self-organization of supramolecular self-assembled porphyrin hollow hexagonal nanoprisms. J Am Chem Soc 127(48):17090–17095

    CAS  PubMed  Google Scholar 

  37. Kim HJ, Zin WC, Lee M (2004) Anion-directed self-assembly of coordination polymer into tunable secondary structure. J Am Chem Soc 126(22):7009–7014

    CAS  PubMed  Google Scholar 

  38. Qiao Y, Lin YY, Zhang SF, Huang JB (2011) Lanthanide-containing photoluminescent materials: from hybrid hydrogel to inorganic nanotubes. Chem Eur J 17(18):5180–5187

    CAS  PubMed  Google Scholar 

  39. Harada A, Takashima Y, Nakahata M (2014) Supramolecular polymeric materials via cyclodextrin-guest interactions. Acc Chem Res 47(7):2128–2140

    CAS  PubMed  Google Scholar 

  40. Brantley JN, Wiggins KM, Bielawski CW (2013) Squeezing new life out of polymers. Angew Chem Int Ed 52(14):3806–3808

    CAS  Google Scholar 

  41. Kirilov P, Gauffre F, Franceschi-Messant S, Perez E, Rico-Lattes I (2009) Rheological characterization of a new type of colloidal dispersion based on nanoparticles of gelled oil. J Phys Chem B 113(32):11101–11108

    CAS  PubMed  Google Scholar 

  42. Yuan JC, Fang XL, Zhang LX, Hong GN, Lin YJ, Zheng QF, Xu YZ, Ruan YH, Weng WG, Xia HP, Chen GH (2012) Multi-responsive self-healing metallo-supramolecular gels based on “click” ligand. J Mater Chem 22(23):11515–11522

    CAS  Google Scholar 

Download references

Funding

The authors gratefully acknowledge the financial support from the Natural Science Foundation of China (NSFC) (21403166, 21706209), the Natural Science Foundation of Shaanxi Province (2016JQ2005, 2017JQ2028), and the Science and Technology Program of Xi’an (2017CGWL01), College Students’ innovation and entrepreneurship training program (201711080004, S201911080057).

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Xue, M., Chen, M., Chang, W. et al. Luminescent lanthanide metallogels: situ fabrication, self-healing and rheological properties. Colloid Polym Sci 298, 233–241 (2020). https://doi.org/10.1007/s00396-020-04598-4

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