Chinese Science Bulletin

, Volume 57, Issue 33, pp 4289–4295 | Cite as

Poly(benzyl ether) dendrons without conventional gelation motifs as a new kind of effective organogelators

  • Yu Feng
  • ZhiXiong Liu
  • LiYing Wang
  • Hui Chen
  • YanMei HeEmail author
  • QingHua FanEmail author
Open Access
Article Progress of Projects Supported by NSFC Special Topic Supramolecular Gel: From Structure to Function


Two poly(benzyl ether) dendrons, decorated in their periphery with nitrile groups, were divergently synthesized and fully characterized. Their gelation properties were studied by using scanning electron microscopy (SEM), X-ray crystal structure analysis and concentration- and temperature-dependent 1H NMR spectroscopy. It was found that the gelation capability of these dendrons was highly dependent on dendron generation, and the second-generation dendron G2-CN proved to be highly efficient organogelator despite the lacking of any conventional gelation motifs, such as amides, long alkyl side chains and steroidal groups. The multiple strong π-π stacking interactions and hydrogen bonding interactions due to the peripheral isophthalonitrile motifs were proved to be the main driving forces to form the self-assembled gel.


dendron organogelator self-assembly 


  1. 1.
    Hirst A R, Smith D K. Dendritic gelators. Top Curr Chem, 2005, 256: 237–373CrossRefGoogle Scholar
  2. 2.
    Smith D K. Dendritic gels: Many arms make light work. Adv Mater, 2006, 18: 2773–2778CrossRefGoogle Scholar
  3. 3.
    Grinstaff M W. Dendritic macromers for hydrogel formation: Tailored materials for ophthalmic, orthopedic, and biotech applications. J Poly Sci A-Poly Chem, 2008, 46: 383–400CrossRefGoogle Scholar
  4. 4.
    Newkome G R, Baker G R, Saunders M J, et al. Two-directional cascade molecules: Synthesis and characterization of [9]-n-[9] a rborols. Chem Soc Chem Commun, 1986: 752–753Google Scholar
  5. 5.
    Newkome G R, Baker G R, Arai S, et al. Synthesis and characterization of two-directional cascade molecules and formation of aqueous gels. J Am Chem Soc, 1990, 112: 8458–8465CrossRefGoogle Scholar
  6. 6.
    Marmillon C, Gauffre F, Majoral J P, et al. Organophosphorus dendrimers as new gelators for hydrogels. Angew Chem Int Ed, 2001, 40: 2626–2629CrossRefGoogle Scholar
  7. 7.
    Jang W D, Jiang D L, Aida T. Dendritic physical gel: Hierarchical self-organization of a peptide-core dendrimer to form a micrometer-scale fibrous assembly. J Am Chem Soc, 2000, 122: 3232–3233CrossRefGoogle Scholar
  8. 8.
    Zubarev E R, Pralle M U, Stupp S I, et al. Self-assembly of dendron rod-coil molecules into nanoribbons. J Am Chem Soc, 2001, 123: 4105–4106CrossRefGoogle Scholar
  9. 9.
    Kim C, Kim K T, Chang Y, et al. Supramolecular assembly of amide dendrons. J Am Chem Soc, 2001, 123: 5586–5587CrossRefGoogle Scholar
  10. 10.
    Partridge K S, Smith D K, Dykes G M, et al. Supramolecular dendritic two-component gel. Chem Commun, 2001, 319-320Google Scholar
  11. 11.
    Huang B Q, Hirst A R, Smith D K, et al. A direct comparison of one- and two-component dendritic self-assembled materials: Elucidating molecular recognition pathways. J Am Chem Soc, 2005, 127: 7130–7139CrossRefGoogle Scholar
  12. 12.
    Ji Y, Luo Y F, Jia X R, et al. A dendron based on natural amino acids: Synthesis and behavior as an organogelator and lyotropic liquid crystal. Angew Chem Int Ed, 2005, 44: 6025–6029CrossRefGoogle Scholar
  13. 13.
    Kuang G C, Ji Y, Jia X R, et al. Self-assembly of amino-acid-based dendrons: Organogels and lyotropic and thermotropic liquid crystals. Chem Mater, 2008, 20: 4173–4175CrossRefGoogle Scholar
  14. 14.
    Kuang G C, Jia X R, Chen E Q, et al. Organogels and liquid crystalline properties of amino acid-based dendrons: A systematic study on structure-property relationship. Chem Mater, 2012, 24: 71–80CrossRefGoogle Scholar
  15. 15.
    Chow H F, Zhang J. Structural diversity of a-amino acid based layer-block dendrons and their layer-block sequence-dependent gelation properties. Chem Eur J, 2005, 11: 5817–5831CrossRefGoogle Scholar
  16. 16.
    Lau K N, Chow H F, Chan M C, et al. Dendronized polymer organo gels from click chemistry: A remarkable gelation property owing to synergistic functional-group binding and dendritic size effects. Angew Chem Int Ed, 2008, 47: 6912–6916CrossRefGoogle Scholar
  17. 17.
    Percec V, Peterca M, Yurchenko M E, et al. Thixotropic twin-dendritic organogelators. Chem Eur J, 2008, 14: 909–918CrossRefGoogle Scholar
  18. 18.
    Yang M, Wang W, Wegner G, et al. Self-assembled structures in organogels of amphiphilic diblock codendrimers. Chem Eur J, 2008, 14: 3330–3337CrossRefGoogle Scholar
  19. 19.
    Duan P F, Liu M H. Design and self-assembly of L-glutamate-based aromatic dendrons as ambidextrous gelators of water and organic solvents. Langmuir 2009, 25: 8706–8713CrossRefGoogle Scholar
  20. 20.
    Chen Y L, Bo Z S, Liu C Y, et al. Dendritic effect on supramolecular self-assembly: Organogels with strong fluorescence emission induced by aggregation. Langmuir, 2009, 25: 8548–8555CrossRefGoogle Scholar
  21. 21.
    Seo M, Kim J H, Kim S Y, et al. Self-association of bis-dendritic organogelators: The effect of dendritic architecture on multivalent cooperative interactions. Chem Eur J, 2010, 16: 2427–2441CrossRefGoogle Scholar
  22. 22.
    Yang X C, Lu R, Gai F Y. Rigid dendritic gelators based on oligocarbazoles. Chem Commun, 2010, 46: 1088–1090CrossRefGoogle Scholar
  23. 23.
    Rajamalli P, Prasad E. Luminescent micro and nanogel formation from AB3 type poly(aryl ether) dendron derivatives without conventional multi-interactive gelation motifs. New J Chem, 2011, 35: 1541–1548CrossRefGoogle Scholar
  24. 24.
    Feng Y, He Y M, Fan Q H, et al. Peripherally dimethyl isophthalate-functionalized poly(benzyl ether) dendrons: A new kind of unprecedented highly efficient organogelators. J Am Chem Soc, 2009, 131: 7950–7951CrossRefGoogle Scholar
  25. 25.
    Chen Q, Zhang D Q, Fan Q H, et al. Light-triggered self-assembly of a spiropyran-functionalized dendron into nano-/micrometer-sized particles and photoresponsive organogel with switchable fluorescence. Adv Funct Mater, 2010, 20: 36–42CrossRefGoogle Scholar
  26. 26.
    Barclay T M, Cordes A W, Oakley R T, et al. Oligothiophenes end-capped by nitriles. Preparation and crystal structures of π,π-dicyanooligothiophenes NC(C4H2S)nCN (n=3–6). Chem Mater, 1997, 9: 981–990CrossRefGoogle Scholar
  27. 27.
    Nishida J, Shio Murai N, Yamashita Y, et al. Preparation, characterization, and FET properties of novel dicyanopyrazinoquinoxaline derivatives. Org Lett, 2004, 6: 2007–2010CrossRefGoogle Scholar
  28. 28.
    Jang K, Kinyanjui J M, Lee D C, et al. Morphological control of one-dimensional nanostructures of t-shaped asymmetric bisphenazine. Chem Mater, 2009, 21: 2070–2076CrossRefGoogle Scholar
  29. 29.
    Eldridge J E, Ferry J D. Studies of the cross-linking process in gelatin gels. III. Dependence of melting point on concentration and molecular weight. J Phys Chem, 1954, 58: 992–995CrossRefGoogle Scholar
  30. 30.
    Feng Y, He Y M, Fan Q H, et al. A liquid-phase approach to functionalized janus dendrimers: Novel soluble supports for organic synthesis. Org Lett, 2007, 9: 2261–2264CrossRefGoogle Scholar
  31. 31.
    Fernández G, Sánchez L, Martín N, et al. Large exTTF-based dendrimers. Self-assembly and peripheral cooperative multiencapsulation of C60. J Am Chem Soc, 2008, 130: 10674–10683CrossRefGoogle Scholar
  32. 32.
    Yang H, Yi T, Li F Y, et al. Switchable fluorescent organogels and mesomorphic superstructure based on naphthalene derivatives. Langmuir, 2007, 23: 8224–8230CrossRefGoogle Scholar

Copyright information

© The Author(s) 2012

Authors and Affiliations

  1. 1.Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of ChemistryChinese Academy of SciencesBeijingChina

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