Abstract
Luminescent polymers without traditional aromatic groups have attracted great attention due to their excellent biocompatibility and promising applications. Understanding of the luminescence mechanism of such polymers, however, is still in its infancy. To further reveal the fluorescence mechanism in depth, two kinds of oligomeric siloxanes were skillfully elaborated and fabricated via a convenient and facile one-pot transesterification polycondensation reaction under catalyst-free conditions. Intriguingly, oligomeric siloxanes bearing nonconventional chromophores show bright blue fluorescence under 365 nm UV lamp illumination. Our preliminary results demonstrate that oxygen clusters, namely, clustering-triggered emission (CTE), can well explain the inherent fluorescence of oligomeric siloxanes. Moreover, intermolecular hydrogen bonds are conducive to the aggregation of the molecular chains. Then, these bonds will facilitate the formation of oxygen clusters, which produce electron cloud overlap to form the unusual chromophores. In addition, the results suggest that the fluorescence intensity of oligomeric siloxanes enhances with increasing concentration. Furthermore, excitation-dependent emission behavior is observed when varying the excitation wavelength of oligomeric siloxanes. It is also found that the luminescence of oligomeric siloxanes could be effectively tuned by the solvent and metal ions.
Access options
Subscribe to Journal
Get full journal access for 1 year
$259.00
only $21.58 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
from$8.99
All prices are NET prices.













References
- 1.
Kelley TW, Baude PF, Gerlach C, Ender DE, Muyres D, Haase MA, et al. Recent progress in organic electronics: materials, devices, and processes. Chem Mater. 2004;16:4413–223.
- 2.
Qiu F, Wang D, Zhu Q, Zhu L, Tong G, Lu Y, et al. Real-time monitoring of anticancer drug release with highly fluorescent star-conjugated copolymer as a drug carrier. Biomacromolecules. 2014;15:1355–64.
- 3.
Prodi L, Bolletta F, Montalti M, Zaccheroni N. Luminescent chemosensors for transition metal ions. Coord Chem Rev. 2000;205:59–83.
- 4.
Yang W, Pan CY, Liu XQ, Wang J. Multiple functional hyperbranched poly(amido amine) nanoparticles: synthesis and application in cell imaging. Biomacromolecules . 2011;12:1523–31.
- 5.
Chen G, Li W, Zhou T, Peng Q, Zhai D, Li H, et al. Conjugation-induced rigidity in twisting molecules: filling the gap between aggregation-caused quenching and aggregation-induced emission. Adv Mater. 2015;27:4496–501.
- 6.
Luo J, Xie Z, Lam JWY, Cheng L, Chen H, Qiu C, et al. Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. Chem commun. 2001;18:1740–1.
- 7.
Shang C, Wei N, Zhuo H, Shao Y, Zhang Q, Zhang Z, et al. Highly emissive poly(maleic anhydride-alt-vinyl pyrrolidone) with molecular weight-dependent and excitation-dependent fluorescence. J Mater Chem C. 2017;5:8082–90.
- 8.
Ye R, Liu Y, Zhang H, Su H, Zhang Y, Xu L, et al. Non-conventional fluorescent biogenic and synthetic polymers without aromatic rings. Polym Chem. 2017;8:1722–7.
- 9.
Zhang Q, Mao Q, Shang C, Chen YN, Peng X, Tan H, et al. Simple aliphatic oximes as nonconventional luminogens with aggregation-induced emission characteristics. J Mater Chem C. 2017;5:3699–705.
- 10.
Wang D, Imae T. Fluorescence emission from dendrimers and its pH dependence. J Am Chem Soc. 2004;126:13204–5.
- 11.
Lee WI, Bae Y, Bard AJ. Strong blue photoluminescence and ECL from OH-terminated PAMAM dendrimers in the absence of gold nanoparticles. J Am Chem Soc. 2004;126:8358–9.
- 12.
Jasmine MJ, Kavitha M, Prasad E. Effect of solvent-controlled aggregation on the intrinsic emission properties of PAMAM dendrimers. J Lumin. 2009;129:506–13.
- 13.
Pastor-Pérez L, Chen Y, Shen Z, Lahoz A, Stiriba SE. Unprecedented blue intrinsic photoluminescence from hyperbranched and linear polyethylenimines: polymer architectures and pH-effects. Macromol Rapid Commun. 2007;28:1404–9.
- 14.
Song G, Lin Y, Zhu Z, Zheng H, Qiao J, He C, et al. Strong fluorescence of poly(N-vinylpyrrolidone) and its oxidized hydrolyzate. Macromol Rapid Commun. 2015;36:278–85.
- 15.
Jayamurugan G, Umesh CP, Jayaraman N. Inherent photoluminescence properties of poly(propyl ether imine) dendrimers. Organ Lett. 2008;10:9–12.
- 16.
Restani RB, Morgado PI, Ribeiro MP, Correia IJ, Aguiar-Ricardo A, Bonifácio VD. Biocompatible polyurea dendrimers with pH-dependent fluorescence. Angew Chem Int Ed. 2012;51:5162–5.
- 17.
Yang W, Pan CY. Synthesis and fluorescent properties of biodegradable hyperbranched poly(amido amine)s. Macromol Rapid Commun. 2009;30:2096–101.
- 18.
Lin Y, Gao JW, Liu HW, Li YS. Synthesis and characterization of hyperbranched poly(ether amide)s with thermoresponsive property and unexpected strong blue photoluminescence. Macromolecules. 2009;42:3237–46.
- 19.
Shiau SF, Juang TY, Chou HW, Liang M. Synthesis and properties of new water-soluble aliphatic hyperbranched poly(amido acids) with high pH-dependent photoluminescence. Polymer. 2013;54:623–30.
- 20.
Wu D, Liu Y, He C, Goh SH. Blue photoluminescence from hyperbranched poly(amino ester)s. Macromolecules. 2005;38:9906–9.
- 21.
Chen X, Liu X, Lei J, Xu L, Zhao Z, Kausar F, et al. Synthesis, clustering-triggered emission, explosive detection and cell imaging of nonaromatic polyurethanes. Mol Sys Des Eng. 2018;3:364–75.
- 22.
Du Y, Yan HX, Niu S, Bai L, Chai F. Facile one-pot synthesis of novel water-soluble fluorescent hyperbranched poly(amino esters). RSC Adv. 2016;6:88030–7.
- 23.
Chen H, Dai W, Huang J, Chen S, Yan XH. Construction of unconventional fluorescent poly(amino ester) polyols as sensing platform for label-free detection of Fe3+ ions and l-cysteine. J Mater Sci. 2018;53:15717–25.
- 24.
Miao X, Liu T, Zhang C, Geng X, Meng Y, Li X. Fluorescent aliphatic hyperbranched polyether: chromophore-free and without any N and P atoms. Phys Chem Chem Phys. 2016;18:4295–9.
- 25.
Zhang Z, Feng S, Zhang J. Facile and efficient synthesis of carbosiloxane dendrimers via orthogonal click chemistry between thiol and ene. Macromol Rapid Commun. 2016;37:318–22.
- 26.
Zhao E, Lam JW, Meng L, Hong Y, Deng H, Bai G, et al. Poly[(maleic anhydride)-alt-(vinyl acetate)]: a pure oxygenic nonconjugated macromolecule with strong light emission and solvatochromic effect. Macromolecules. 2014;48:64–71.
- 27.
Du Y, Feng Y, Yan HX, Huang W, Yuan L, Bai L. Fluorescence emission from hyperbranched polycarbonate without conventional chromohpores. J Photo Photobio A. 2018;364:415–23.
- 28.
Huang W, Yan HX, Niu S, Du Y, Yuan L. Unprecedented strong blue photoluminescence from hyperbranched polycarbonate: From its fluorescence mechanism to applications. J Polym Sci Poly Chem. 2017;55:3690–6.
- 29.
Zhou X, Luo W, Nie H, Xu L, Hu R, Zhao Z, et al. Oligo(maleic anhydride)s: a platform for unveiling the mechanism of clusteroluminescence of non-aromatic polymers. J Mater Chem C. 2017;5:4775–9.
- 30.
Zhou Q, Cao B, Zhu C, Xu S, Gong Y, Yuan WZ, et al. Clustering-triggered emission of nonconjugated polyacrylonitrile. Small . 2016;12:6586–92.
- 31.
Lu H, Feng L, Li S, Zhang J, Lu H, Feng SY. Unexpected strong blue photoluminescence produced from the aggregation of unconventional chromophores in novel siloxane-poly(amidoamine) dendrimers. Macromolecules. 2015;48:476–82.
- 32.
Lu H, Hu Z, Feng SY. Nonconventional luminescence enhanced by silicone-induced aggregation. Chem-Asian J. 2017;12:1213–7.
- 33.
Liu B, Wang YL, Bai W, Xu JT, Xu ZK, Yang K, et al. Fluorescent linear CO2-derived poly(hydroxyurethane) for cool white LED. J Mater Chem C. 2017;5:4892–8.
- 34.
Zhang YW, Zhang Y. Nonconventional macromolecular luminogens with aggregation-induced emission characteristics. J Polym Sci Poly Chem. 2017;55:560–74.
- 35.
Du Y, Yan HX, Huang W, Chai F, Niu S. Unanticipated strong blue photoluminescence from fully biobased aliphatic hyperbranched polyesters. ACS Sustain Chem Eng. 2017;5:6139–47.
- 36.
Niu S, Yan HX, Chen Z, Li S, Xu P, Zhi X. Unanticipated bright blue fluorescence produced from novel hyperbranched polysiloxanes carrying unconjugated carbon-carbon double bonds and hydroxyl groups. Polym Chem. 2016;7:3747–55.
- 37.
Niu S, Yan HX, Chen Z, Yuan L, Liu T, Liu C. Water-soluble blue fluorescence-emitting hyperbranched polysiloxanes simultaneously containing hydroxyl and primary amine groups. Macromol Rapid Commun. 2016;37:136–42.
- 38.
Niu S, Yan HX, Li S, Xu P, Zhi X, Li T. Bright blue photoluminescence emitted from the novel hyperbranched polysiloxane-containing unconventional chromogens. Macromol Chem Phys. 2016;217:1185–90.
- 39.
Zhang T, Howell BA, Dumitrascu A, Martin SJ, Smith PB. Synthesis and characterization of glycerol-adipic acid hyperbranched polyesters. Polymer. 2014;55:5065–72.
- 40.
Asakuma Y, Maeda K, Kuramochi H, Fukui K. Theoretical study of the transesterification of triglycerides to biodiesel fuel. Fuel. 2009;88:786–91.
- 41.
Niu S, Yan H, Chen Z, Du Y, Huang W, Bai L, et al. Hydrosoluble aliphatic tertiary amine-containing hyperbranched polysiloxanes with bright blue photoluminescence. RSC Adv. 2016;6:106742–53.
- 42.
Li Q, Tang Y, Hu W, Li Z. Fluorescence of nonaromatic organic systems and room temperature phosphorescence of organic luminogens: the intrinsic principle and recent progress. Small. 2018;14:1801560.
- 43.
Chen X, Luo W, Ma H, Peng Q, Yuan WZ, Zhang Y. Prevalent intrinsic emission from nonaromatic amino acids and poly(amino acids). Sci Chin Chem. 2018;61:351–9.
- 44.
Tomalia DA, Klajnert-Maculewicz B, Johnson KAM, Brinkman HF, Janaszewska A, Hedstrand DM. Non-traditional intrinsic luminescence: inexplicable blue fluorescence observed for dendrimers, macromolecules and small molecular structures lacking traditional/conventional luminophores. Prog Polym Sci. 2019;90:35–117.
- 45.
Niu S, Yan HX, Li S, Tang C, Chen Z, Zhi X, et al. A multifunctional silicon-containing hyperbranched epoxy: controlled synthesis, toughening bismaleimide and fluorescent properties. J Mater Chem C. 2016;4:6881–93.
- 46.
Lu H, Zhang J, Feng S. Controllable photophysical properties and self-assembly of siloxane-poly(amidoamine) dendrimers. Phys Chem Chem Phys. 2015;17:26783–9.
- 47.
Yan J, Zheng B, Pan D, Yang R, Xu Y, Wang L, et al. Unexpected fluorescence from polymers containing dithio/amino-succinimides. Polym Chem. 2015;6:6133–9.
- 48.
Wang Y, Bin X, Chen, Zheng S, Zhang Y, Yuan W. Emission and emissive mechanism of nonaromatic oxygen clusters. Macromol Rapid Commun. 2018;39:1800528.
- 49.
Li Z, Zhang L, Zhao W, Li X, Guo Y, Yu M, et al. Fluoranthene-based pyridine as fluorescent chemosensor for Fe3+. Inorg Chem Common. 2011;14:1656–8.
- 50.
Zhang S, Li J, Zeng M, Xu J, Wang X, Hu W. Polymer nanodots of graphitic carbon nitride as effective fluorescent probes for the detection of Fe3+ and Cu2+ ions. Nanoscale. 2014;6:4157–62.
Acknowledgements
This work is sponsored by the National Natural Science Foundation of China (21875188), Natural Science Basic Research Plan in Shaanxi Province of China (Program No. 2018JM2024) and the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University (CX201719).
Author information
Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare on conflict of interest.
Additional information
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
About this article
Cite this article
Du, Y., Bai, T., Ding, F. et al. The inherent blue luminescence from oligomeric siloxanes. Polym J 51, 869–882 (2019). https://doi.org/10.1038/s41428-019-0208-1
Received:
Revised:
Accepted:
Published:
Issue Date:
Further reading
-
Silicon-assisted unconventional fluorescence from organosilicon materials
Coordination Chemistry Reviews (2021)
-
Clustering-triggered Emission of Nonaromatic Polymers with Multitype Heteroatoms and Effective Hydrogen Bonding
Chemical Research in Chinese Universities (2021)
-
Polymerization-induced emission
Materials Horizons (2020)
-
Glutathione-Functionalized Organosilicon Oxide Nanoparticles for Bioimaging and Forensics
ACS Applied Nano Materials (2020)