Abstract
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.
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Hirst A R, Smith D K. Dendritic gelators. Top Curr Chem, 2005, 256: 237–373
Smith D K. Dendritic gels: Many arms make light work. Adv Mater, 2006, 18: 2773–2778
Grinstaff M W. Dendritic macromers for hydrogel formation: Tailored materials for ophthalmic, orthopedic, and biotech applications. J Poly Sci A-Poly Chem, 2008, 46: 383–400
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: 752–753
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: 8458–8465
Marmillon C, Gauffre F, Majoral J P, et al. Organophosphorus dendrimers as new gelators for hydrogels. Angew Chem Int Ed, 2001, 40: 2626–2629
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: 3232–3233
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: 4105–4106
Kim C, Kim K T, Chang Y, et al. Supramolecular assembly of amide dendrons. J Am Chem Soc, 2001, 123: 5586–5587
Partridge K S, Smith D K, Dykes G M, et al. Supramolecular dendritic two-component gel. Chem Commun, 2001, 319-320
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: 7130–7139
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: 6025–6029
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: 4173–4175
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: 71–80
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: 5817–5831
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: 6912–6916
Percec V, Peterca M, Yurchenko M E, et al. Thixotropic twin-dendritic organogelators. Chem Eur J, 2008, 14: 909–918
Yang M, Wang W, Wegner G, et al. Self-assembled structures in organogels of amphiphilic diblock codendrimers. Chem Eur J, 2008, 14: 3330–3337
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: 8706–8713
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: 8548–8555
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: 2427–2441
Yang X C, Lu R, Gai F Y. Rigid dendritic gelators based on oligocarbazoles. Chem Commun, 2010, 46: 1088–1090
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: 1541–1548
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: 7950–7951
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: 36–42
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: 981–990
Nishida J, Shio Murai N, Yamashita Y, et al. Preparation, characterization, and FET properties of novel dicyanopyrazinoquinoxaline derivatives. Org Lett, 2004, 6: 2007–2010
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: 2070–2076
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: 992–995
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: 2261–2264
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: 10674–10683
Yang H, Yi T, Li F Y, et al. Switchable fluorescent organogels and mesomorphic superstructure based on naphthalene derivatives. Langmuir, 2007, 23: 8224–8230
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Feng, Y., Liu, Z., Wang, L. et al. Poly(benzyl ether) dendrons without conventional gelation motifs as a new kind of effective organogelators. Chin. Sci. Bull. 57, 4289–4295 (2012). https://doi.org/10.1007/s11434-012-5479-2
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DOI: https://doi.org/10.1007/s11434-012-5479-2