Advertisement

Journal of Chemical Sciences

, 130:141 | Cite as

Self-assembly of tetraphenylethylene-based dendron into blue fluorescent nanoparticles with aggregation induced enhanced emission\(^{\S }\)

  • Nithiyanandan Krishnan
  • M A Hanna Ameena
  • Siriki Atchimnaidu
  • Devanathan Perumal
  • Murali Golla
  • Jithu Krishna
  • Reji Varghese
Regular Article

Abstract

Luminescent organic nanoassemblies have received great attention in recent years due to their potential applications in material science and bioimaging. Since most of the fluorophores undergo aggregation-caused quenching in the solid state, their technological applications are limited. Hence, there is a high demand for the design of fluorophores which show enhanced emission in the aggregated and solid states. Herein we report the design and synthesis of a tetraphenylethylene based dendron through multistep organic reactions. Very weak emission is observed for the dendron in the molecularly dissolved state, which is attributed to the rotational relaxation of intramolecular \(\hbox {C}(\hbox {sp}^{2})\)\(\hbox {C}(\hbox {sp}^{2})\) bond rotation in the excited state. The aggregates of the dendron are prepared with the addition of a ‘poor’ solvent into a solution of the dendron in a ‘good’ solvent. A huge enhancement in fluorescence is observed in the aggregated state, which is attributed to the restriction of intramolecular \(\hbox {C}(\hbox {sp}^{2})\)\(\hbox {C}(\hbox {sp}^{2})\) bond rotation and makes the radiative decay as the main decay channel for the aggregated state. The induced self-assembly of the dendron with the addition of ‘poor’ solvent results in the formation of emissive nanoparticles. We hope the blue emissive nanoparticles may find applications in material science and bioimaging.

Graphical Abstract

SYNOPSIS Synthesis of a new tetraphenylethylene-based dendron using multistep organic reactions is reported. Self-assembly of the dendron into nanoparticles is achieved with the addition of a “poor” solvent (water) into a solution of the dendron in “good” solvent (DMSO). A strong aggregation induced enhanced emission is observed for the nanoparticle due to the restriction of intramolecular \(\hbox {C}(\hbox {sp}^{2})\)\(\hbox {C}(\hbox {sp}^{2})\) bond rotation in the aggregated state.

Keywords

Self-assembly fluorescence nanoparticles 

Notes

Acknowledgements

Financial support from KSCSTE (KSYSA Grant) is gratefully acknowledged. We thank UGC (N. K.) and CSIR (D. P.) for research fellowships.

References

  1. 1.
    (a) Magginia L and Bonifaz D 2012 Hierarchized Luminescent Organic Architectures: Design, Synthesis, Self-assembly, Self-organization and Functions Chem. Soc. Rev. 41 211; (b) Messmore B W, Hulvat J F, Sone E D and Stupp S I 2004 Synthesis, Self-Assembly, and Characterization of Supramolecular Polymers from Electroactive Dendron Rodcoil Molecules J. Am. Chem. Soc. 126 14452; (c) Han J, You J, Li X, Duan P and Liu M 2017 Full-Color Tunable Circularly Polarized Luminescent Nano-assemblies of Achiral AIEgens in Confined Chiral Nanotubes Adv. Mater. 29 1606503Google Scholar
  2. 2.
    (a) Figueira T M, Rosso P G D, Trattnig R, Sax S, List E J W and Müllen K 2010 Designed Suppression of Aggregation in Polypyrene: Toward High-performance Blue-light-emitting Diodes Adv. Mater. 22 990; (b) Shiraishi K, Kashiwabara T, Sanji T and Tanaka M 2009 Aggregation Induced Emission of Dendritic Phosphole oxides New J. Chem. 33 1680; (c) Miyake J and Chujo Y 2008 Thermally Stabilized Blue Luminescent Poly(p-phenylene)s Covered with Polyhedral Oligomeric Silsesquioxanes Macromol. Rapid Commun. 29 86; (d) Satrijo A, Kooi S E and Swager T M 2007 Enhanced Luminescence from Emissive Defects in Aggregated Conjugated Polymers Macromolecules 40 8833; (e) Wang J, Zhao Y, Dou Y C, Sun H, Xu P, Ye K, Zhang J, Jiang S, Li F and Wang Y 2007 Alkyl and Dendron Substituted Quinacridones: Synthesis, Structures, and Luminescent Properties J. Phys. Chem. B 111 5082Google Scholar
  3. 3.
    Masai H, Terao J, Seki S, Nakashima S, Kiguchi M, Okoshi K, Fujihara T and Tsuji Y 2014 Synthesis of One-Dimensional Metal-Containing Insulated Molecular Wire with Versatile Properties Directed toward Molecular Electronics Materials J. Am. Chem. Soc. 136 1742; (b) Terao J, Homma K, Konoshima Y, Imoto R, Masai H, Matsuda W, Seki S, Fujiharaa T and Tsujia Y 2014 Synthesis of Functionalized Insulated Molecular Wires by Polymerization of an Insulated p-Conjugated Monomer Chem. Commun. 50 658CrossRefGoogle Scholar
  4. 4.
    Liang J, Tang B Z and Liu B 2015 Specific Light-up Bioprobes Based on AIEgen Conjugates Chem. Soc. Rev. 44 2798; (b) Hong Y, Lama J W Y and Tang B Z 2009 Aggregation-induced Emission: Phenomenon, Mechanism and Applications Chem. Commun. 4332CrossRefGoogle Scholar
  5. 5.
    Hong Y, Lama J W Y and Tang B Z 2011 Aggregation-induced Emission Chem. Soc. Rev. 40 5361CrossRefGoogle Scholar
  6. 6.
    Lee Y T, Chang Y T, Chen C T and Chen C T 2016 The First Aggregation-induced Emission Fluorophore as a Solution Processed Host Material in Hybrid White Organic Light-emitting Diodes J. Mater. Chem. C 4 7020; (b) Hong Y 2016 Aggregation-induced Emission-Fluorophores and Applications Methods Appl. Fluoresc. 4 022003Google Scholar
  7. 7.
    Ding D, Li K, Liu B and Tang B Z 2013 Bioprobes Based on AIE Fluorogens Acc. Chem. Res. 46 2441; (b) Zhao Y, Yu C Y Y, Kwok R T K, Chen Y, Chen S, Lamab J W Y and Tang B Z 2015 Photostable AIE Fluorogens for Accurate and Sensitive Detection of S-phase DNA Synthesis and Cell Proliferation J. Mater. Chem. B 3 4993Google Scholar
  8. 8.
    Liu Y, Deng C, Tang L, Qin A, Hu R, Sun J Z and Tang B Z 2011 Specific Detection of D-Glucose by a Tetraphenylethene-Based Fluorescent Sensor J. Am. Chem. Soc. 133 660; (b) Shi H, Liu J, Geng J, Tang B Z and Liu B 2012 Specific Detection of Integrin Rv\(\upbeta \)3 by Light-up Bioprobe with Aggregation-Induced Emission Characteristics J. Am. Chem. Soc. 134 9569Google Scholar
  9. 9.
    La D D, Bho sale S V, Jones L A and Bhosale S V 2018 Tetraphenylethylene-Based AIE-Active Probes for Sensing Applications ACS Appl. Mater. Interfaces 10 12189; (b) Cai Y, Shi C, Zhang H, Chen B, Samedov K, Chen M, Wang Z, Zhao Z, Gu X, Ma D, Qin A and Tang B Z 2018 Sulfur-bridged Tetraphenylethylene AIEgens for Deep-blue Organic Light-emitting Diodes J. Mater. Chem. C 6 6534Google Scholar
  10. 10.
    Albert S K, Thelu H V P, Golla M, Krishnan N, Chaudhary S and Varghese R 2014 Self-Assembly of DNA–Oligo(p-phenyleneethynylene) Hybrid Amphiphiles into Surface-Engineered Vesicles with Enhanced Emission Angew. Chem. Int. Ed. 53 8352CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2018

Authors and Affiliations

  • Nithiyanandan Krishnan
    • 1
  • M A Hanna Ameena
    • 1
  • Siriki Atchimnaidu
    • 1
  • Devanathan Perumal
    • 1
  • Murali Golla
    • 1
  • Jithu Krishna
    • 1
  • Reji Varghese
    • 1
  1. 1.School of ChemistryIndian Institute of Science Education and Research (IISER) ThiruvananthapuramThiruvananthapuramIndia

Personalised recommendations