Polycyclotrimerization of Dinitriles: A New Polymerization Route for the Construction of Soluble Nitrogen-Rich Polytriazines with Hyperbranched Structures and Functional Properties
Abstract
A new synthetic route to nitrogen-rich hyperbranched polymers is developed. The polycyclotrimerizations of dinitriles [NC–C 6 H 4 –O(CH 2 ) 4 O–C 6 H 4 –CN and NC–C 6 H 4 –O(CH 2 ) 4 O–Ar–O(CH 2 ) 4 O–C 6 H 4 –CN Ar = isopropylidenebis(1,4-phenylene), 9,9-fluorenylenebis(1,4-phenylene) and 1,2-diphenylethenylenebis(1,4-phenylene)] catalyzed by trifluoromethanesulfonic acid proceed smoothly in 1,2-dichlorobenzene at room temperature, affording hyperbranched poly(triazine)s with high degree of branching (DB ∼63%) in high yields (up to 74.7%). All the polymers are soluble and film-forming. The polymers are thermally and morphologically stable, showing high thermal-degradation and glass-transition temperatures up to 363 and 126.5 °C, respectively. They are optically transparent, allowing almost all visible and IR lights to transmit through. The polymer thin films show high refractive indices ( n = 1.7456–1.5857) in a wide spectral region (400–1600 nm) as well as high Abbe numbers (ν D ′ up to 187.4) and low optical dispersions ( D ′ down to 0.005). Polymerization of tetraphenylethene-containing dinitrile generates a polymer with aggregation-induced emission characteristic, enabling it to be utilized as a sensitive and selective fluorescent chemosensor for ruthenium(III) ion detection.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Cites
Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole
Luo, J., Xie, Z., Lam, J. W. Y., Cheng, L., Tang, B. Z., Chen, H., Qiu, C., Kwok, H. S., Zhan, X., Liu, Y., et al. (2001) · Chemical Communications · doi:10.1039/b105159h · Cited by 8,358 · see citing works
Self-citationHong, Y., Lam, J. W. Y., & Tang, B. Z. (2011) · Chemical Society Reviews · doi:10.1039/c1cs15113d · Cited by 6,363 · see citing works
Self-citationPhotophysics of aromatic molecules
Sharnoff, M. (1971) · Journal of Luminescence · doi:10.1016/0022-2313(71)90011-1 · Cited by 4,509 · see citing works
Aggregation-induced emission: phenomenon, mechanism and applications
Hong, Y., Lam, J. W. Y., & Tang, B. Z. (2009) · Chemical Communications · doi:10.1039/b904665h · Cited by 4,125 · see citing works
Self-citationPhotophysics of aromatic molecules
Birks, J. B. (1970) · Cited by 3,326 · see citing works
Porous, Covalent Triazine‐Based Frameworks Prepared by Ionothermal Synthesis
Kuhn, P., Antonietti, M., & Thomas, A. (2008) · Angewandte Chemie International Edition · doi:10.1002/anie.200705710 · Cited by 2,641 · see citing works
Young, R. J., & Lovell, P. A. (1981) · Springer eBooks · doi:10.1007/978-1-4615-3478-5 · Cited by 2,120 · see citing works
Hyperbranched polymers: from synthesis to applications
Gao, C., & Yan, D. (2004) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2003.12.002 · Cited by 2,046 · see citing works
Coordination Assemblies from a Pd(II)-Cornered Square Complex
Fujita, M., Tominaga, M., Hori, A., & Therrien, B. (2005) · Accounts of Chemical Research · doi:10.1021/ar040153h · Cited by 2,024 · see citing works
Acetylenic Polymers: Syntheses, Structures, and Functions
Liu, J., Lam, J. W. Y., & Tang, B. Z. (2009) · Chemical Reviews · doi:10.1021/cr900149d · Cited by 1,198 · see citing works
Self-citationVoit, B. I., & Lederer, A. (2009) · Chemical Reviews · doi:10.1021/cr900068q · Cited by 1,184 · see citing works
One-step synthesis of hyperbranched dendritic polyesters
Hawker, C. J., Lee, R., & Fréchet, J. M. J. (1991) · Journal of the American Chemical Society · doi:10.1021/ja00012a030 · Cited by 1,122 · see citing works
Controlled Synthesis of Hyperbranched Polyglycerols by Ring-Opening Multibranching Polymerization
Sunder, A., Hanselmann, R., Frey, H., & Mülhaupt, R. (1999) · Macromolecules · doi:10.1021/ma990090w · Cited by 1,050 · see citing works
Hyperbranched polymers: a promising new class of materials
Jikei, M., & Kakimoto, M. (2001) · Progress in Polymer Science · doi:10.1016/s0079-6700(01)00018-1 · Cited by 923 · see citing works
Self-Condensing Vinyl Polymerization: An Approach to Dendritic Materials
Fréchet, J. M. J., Henmi, M., Gitsov, I., et al. (1995) · Science · doi:10.1126/science.269.5227.1080 · Cited by 851 · see citing works
Ren, S., Bojdys, M. J., Dawson, R., Laybourn, A., Khimyak, Y. Z., Adams, D. J., & Cooper, A. I. (2012) · Advanced Materials · doi:10.1002/adma.201200751 · Cited by 762 · see citing works
A net-based approach to coordination polymers †
Robson, R. (2000) · Journal of the Chemical Society Dalton Transactions · doi:10.1039/b003591m · Cited by 726 · see citing works
Lam, J. W. Y., & Tang, B. Z. (2005) · Accounts of Chemical Research · doi:10.1021/ar040012f · Cited by 726 · see citing works
Self-citationRecent advances in [2+2+2] cycloaddition reactions
Domı́nguez, G., & Pérez‐Castells, J. (2011) · Chemical Society Reviews · doi:10.1039/c1cs15029d · Cited by 606 · see citing works
Qin, A., Lam, J. W. Y., & Tang, B. Z. (2010) · Chemical Society Reviews · doi:10.1039/b909064a · Cited by 590 · see citing works
Self-citationBojdys, M. J., Jeromenok, J., Thomas, A., et al. (2010) · Advanced Materials · doi:10.1002/adma.200903436 · Cited by 571 · see citing works
Kuhn, P., Forget, A., Su, D., et al. (2008) · Journal of the American Chemical Society · doi:10.1021/ja803708s · Cited by 556 · see citing works
Hawker, C. J., Fréchet, J. M. J., Grubbs, R. B., & Dao, J. (1995) · Journal of the American Chemical Society · doi:10.1021/ja00148a027 · Cited by 543 · see citing works
Synthesis of Branched and Hyperbranched Polystyrenes
Gaynor, S. G., Edelman, S., & Matyjaszewski, K. A. (1996) · Macromolecules · doi:10.1021/ma9513877 · Cited by 480 · see citing works
Luminogenic polymers with aggregation-induced emission characteristics
Qin, A., Lam, J. W. Y., & Tang, B. Z. (2011) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2011.08.002 · Cited by 441 · see citing works
Self-citationHyperbranched polymers—All problems solved after 15 years of research?
Voit, B. I. (2005) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20821 · Cited by 381 · see citing works
Matyjaszewski, K. A., Gaynor, S. G., Kulfan, A., et al. (1997) · Macromolecules · doi:10.1021/ma970359g · Cited by 344 · see citing works
Ranganathan, A., Pedireddi, V. R., & Rao, C. N. R. (1999) · Journal of the American Chemical Society · doi:10.1021/ja983928o · Cited by 341 · see citing works
Aggregation-induced Emission of Silole Molecules and Polymers: Fundamental and Applications
Liu, J., Lam, J. W. Y., & Tang, B. Z. (2009) · Journal of Inorganic and Organometallic Polymers and Materials · doi:10.1007/s10904-009-9282-8 · Cited by 331 · see citing works
Self-citationLiu, J., Zhong, Y., Lü, P., Hong, Y., Lam, J. W. Y., Mahtab, F., Yu, Y., Wong, K. S., & Tang, B. Z. (2010) · Polymer Chemistry · doi:10.1039/c0py00046a · Cited by 316 · see citing works
Self-citationYan, D., Müller, A. H. E., & Matyjaszewski, K. A. (1997) · Macromolecules · doi:10.1021/ma961919z · Cited by 301 · see citing works
Click Polymerization: Progresses, Challenges, and Opportunities
Qin, A., Lam, J. W. Y., & Tang, B. Z. (2010) · Macromolecules · doi:10.1021/ma101064u · Cited by 281 · see citing works
Self-citationKokado, K., & Chujo, Y. (2009) · Macromolecules · doi:10.1021/ma8027358 · Cited by 264 · see citing works
(2011) · Wiley eBooks · doi:10.1002/9780470929001 · Cited by 261 · see citing works
One-pot synthesis of hyperbranched polyethers
Uhrich, K. E., Hawker, C. J., Fréchet, J. M. J., et al. (1992) · Macromolecules · doi:10.1021/ma00044a019 · Cited by 239 · see citing works
Introduction to the Chemistry of Heterocyclic Compounds
Acheson, R. M. (1967) · Andalas University Repository (Andalas University) · Cited by 238 · see citing works
Hu, R., Maldonado, J., Rodriguez, M. A., Deng, C., Jim, C. K. W., Lam, J. W. Y., Yuen, M. M. F., Ramos‐Ortíz, G., & Tang, B. Z. (2011) · Journal of Materials Chemistry · doi:10.1039/c1jm13556b · Cited by 238 · see citing works
Self-citationLiu, J., Zhong, Y., Lam, J. W. Y., Lü, P., Hong, Y., Yu, Y., Yue, Y., Mahtab, F., Sung, H. H. Y., Williams, I. D., et al. (2010) · Macromolecules · doi:10.1021/ma902432m · Cited by 223 · see citing works
Self-citationπ‐Conjugated Oligo‐(p‐phenylenevinylene) Rosettes and Their Tubular Self‐Assembly
Jonkheijm, P., Miura, A., Zdanowska, M., et al. (2003) · Angewandte Chemie International Edition · doi:10.1002/anie.200352790 · Cited by 211 · see citing works
Aggregation-Enhanced Emissions of Intramolecular Excimers in Disubstituted Polyacetylenes
Qin, A., Jim, C. K. W., Tang, Y., Lam, J. W. Y., Liu, J., Mahtab, F., Gao, P., & Tang, B. Z. (2008) · The Journal of Physical Chemistry B · doi:10.1021/jp800296t · Cited by 175 · see citing works
Self-citationArchitecture of nanostructured polymers
Ishizu, K., Tsubaki, K., Mori, A., et al. (2002) · Progress in Polymer Science · doi:10.1016/s0079-6700(02)00025-4 · Cited by 165 · see citing works
Hyperbranched methacrylates by self‐condensing group transfer polymerization
Simon, P. F. W., Radke, W., & Müller, A. H. E. (1997) · Macromolecular Rapid Communications · doi:10.1002/marc.1997.030180915 · Cited by 140 · see citing works
Malek, N., Maris, T., Simard, M. G., et al. (2005) · Journal of the American Chemical Society · doi:10.1021/ja042233m · Cited by 134 · see citing works
Control of molecular interactions by the hollow of coordination cages
Maurizot, V., Yoshizawa, M., Kawano, M., et al. (2006) · Dalton Transactions · doi:10.1039/b516548m · Cited by 112 · see citing works
Li, Z., Qin, A., Lam, J. W. Y., et al. (2006) · Macromolecules · doi:10.1021/ma051924f · Cited by 110 · see citing works
Self-citationHyperbranched Nanomolecules: Regular Polystyrene Dendrigrafts
Muchtar, Z., Schappacher, M., & Deffieux, A. (2001) · Macromolecules · doi:10.1021/ma010429q · Cited by 106 · see citing works
Development of DSM's hybrane® hyperbranched polyesteramides
Froehling, P. (2004) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20113 · Cited by 99 · see citing works
Functional Hyperbranched Macromolecules Constructed from Acetylenic Triple-Bond Building Blocks
Häußler, M., & Tang, B. Z. (2007) · Advances in polymer science · doi:10.1007/12_2007_112 · Cited by 95 · see citing works
Self-citationSynthesis and Photomodulation of Rigid Polyphenylene Dendrimers with an Azobenzene Core
Grebel-Koehler, D., Liu, D., Feyter, S. D., et al. (2003) · Macromolecules · doi:10.1021/ma021135n · Cited by 89 · see citing works
Suzuki, M., Yoshida, S., Shiraga, K., et al. (1998) · Macromolecules · doi:10.1021/ma971222t · Cited by 88 · see citing works
Peng, H., Cheng, L., Luo, J., et al. (2002) · Macromolecules · doi:10.1021/ma020180s · Cited by 87 · see citing works
Yan, D., Zhou, Z., & Müller, A. H. E. (1999) · Macromolecules · doi:10.1021/ma9716488 · Cited by 86 · see citing works
Dong, H., Zheng, R., Lam, J. W. Y., et al. (2005) · Macromolecules · doi:10.1021/ma050342v · Cited by 81 · see citing works
Self-citationNasef, M. M., Saidi, H., Nor, H. M., & Foo, O. M. (2000) · Journal of Applied Polymer Science · doi:10.1002/(sici)1097-4628(20000404)76:1 · Cited by 79 · see citing works
Baskaran, D. (2003) · Polymer · doi:10.1016/s0032-3861(03)00032-6 · Cited by 77 · see citing works
Häußler, M., Qin, A., & Tang, B. Z. (2007) · Polymer · doi:10.1016/j.polymer.2007.08.044 · Cited by 72 · see citing works
Self-citationQin, A., Lam, J. W. Y., Dong, H., Lu, W., Jim, C. K. W., Dong, Y. Q., Häußler, M., Sung, H. H. Y., Williams, I. D., Wong, G. K., et al. (2007) · Macromolecules · doi:10.1021/ma070200w · Cited by 71 · see citing works
Self-citationRecent Progress in the Development of New Acetylenic Polymers
Hu, R., Lam, J. W. Y., & Tang, B. Z. (2012) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201200389 · Cited by 71 · see citing works
Self-citationHäußler, M., Liu, J., Zheng, R., et al. (2007) · Macromolecules · doi:10.1021/ma062346l · Cited by 68 · see citing works
Przybyla, C., & Fink, G. (1999) · Acta Polymerica · doi:10.1002/(sici)1521-4044(19990201)50:2/3 · Cited by 64 · see citing works
Hyperbranched fluorocopolymers by atom transfer radical self‐condensing vinyl copolymerization
Cheng, C., Wooley, K. L., & Khoshdel, E. (2005) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20987 · Cited by 62 · see citing works
Synthesis of 1,3,5-triazines in solvent-free conditions catalysed by silica-supported lewis acids
Díaz‐Ortiz, Á., de la Hoz, A., Moreno, A., et al. (2002) · Green Chemistry · doi:10.1039/b202014a · Cited by 61 · see citing works
Liu, J., Zheng, R., Tang, Y., et al. (2007) · Macromolecules · doi:10.1021/ma071062d · Cited by 57 · see citing works
Jim, C. K. W., Qin, A., Lam, J. W. Y., et al. (2009) · Macromolecules · doi:10.1021/ma900076z · Cited by 46 · see citing works
Self-citationZheng, R., Häußler, M., Dong, H., et al. (2006) · Macromolecules · doi:10.1021/ma061127x · Cited by 44 · see citing works
Triazine‐containing benzoxazine and its high‐performance polymer
Wang, D., Li, B., Zhang, Y., et al. (2012) · Journal of Applied Polymer Science · doi:10.1002/app.37816 · Cited by 43 · see citing works
Xu, F., Sun, J., Yan, H., et al. (2000) · Synthetic Communications · doi:10.1080/00397910008087119 · Cited by 38 · see citing works
Li, Z., Lam, J. W. Y., Dong, Y., et al. (2006) · Macromolecules · doi:10.1021/ma0601823 · Cited by 37 · see citing works
Self-citationZheng, R., Dong, H., Peng, H., et al. (2004) · Macromolecules · doi:10.1021/ma049871+ · Cited by 37 · see citing works
López, G., Sánchez, G., Garcı́a, G., et al. (1991) · Angewandte Chemie International Edition in English · doi:10.1002/anie.199107161 · Cited by 36 · see citing works
Fujita, M., Takemura, A., Ono, H., Kajiyama, M., Hayashi, S., & Mizumachi, H. (2000) · Journal of Applied Polymer Science · doi:10.1002/(sici)1097-4628(20000321)75:12 · Cited by 36 · see citing works
Häußler, M., Lam, J. W. Y., Zheng, R., et al. (2003) · Comptes Rendus Chimie · doi:10.1016/j.crci.2003.06.003 · Cited by 36 · see citing works
Self-citationNetworking a hollow cage via guest coordination
Kobayashi, Y., Kawano, M., & Fujita, M. (2006) · Chemical Communications · doi:10.1039/b612562j · Cited by 31 · see citing works
Armstrong, D. R., Henderson, K. W., MacGregor, M., et al. (1995) · Journal of Organometallic Chemistry · doi:10.1016/0022-328x(94)05030-f · Cited by 27 · see citing works
Bringmann, G. (1977) · Angewandte Chemie · doi:10.1002/ange.19770890832 · Cited by 27 · see citing works
(2008) · Chemistry International · doi:10.1515/ci.2008.30.1.33 · Cited by 25 · see citing works
Liu, J., Zhang, L., Lam, J. W. Y., et al. (2009) · Macromolecules · doi:10.1021/ma901247q · Cited by 24 · see citing works
Self-citationCatalytic Cyclotrimerization of Arylnitriles Using the Novel Samarium (II) Complexes as Catalysts
Xu, F., Zhu, X., Shen, Q., et al. (2002) · Chinese Journal of Chemistry · doi:10.1002/cjoc.20020201130 · Cited by 23 · see citing works
Zhang, W., Liao, S., Xu, Y. P., et al. (1997) · Synthetic Communications · doi:10.1080/00397919708005919 · Cited by 17 · see citing works
Preparation of poly(?-caprolactone)-co-poly(acrylic acid) by radiation-induced grafting
S�derg�rd, A. (1998) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/(sici)1099-0518(199808)36:11 · Cited by 16 · see citing works
Reactions of Bis(silyl-substituted) Methyllithium with α-Hydrogen-free Nitriles into 1,3,5-Triazines
Chen, X., Bai, S., Wang, L., et al. (2005) · Heterocycles · doi:10.3987/com-05-10357 · Cited by 15 · see citing works
Cyclotrimerization of nitriles catalyzed by Li3N
Deng, Z. (2004) · Chinese Science Bulletin · doi:10.1360/03wb0128 · Cited by 14 · see citing works
Koppes, W. M., & Adolph, H. G. (1981) · The Journal of Organic Chemistry · doi:10.1021/jo00315a034 · Cited by 11 · see citing works
Progress in the Synthesis ofs-Triazine Derivative
Luo, H., Wang, H., Zeng, Z., et al. (2013) · Chinese Journal of Organic Chemistry · doi:10.6023/cjoc201209024 · Cited by 4 · see citing works
Binding and endocytosis of monoterbium transferrin by K562 cells
Zhao, C. (2003) · Chinese Science Bulletin · doi:10.1360/03tb9025 · Cited by 3 · see citing works
New developments in hyperbranched polymers
Voit, B. (2000) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/1099-0518(20000715)38:14
Flagged first, then by citations
Cited by
Sorted by citations
Aggregation-Induced Emission: Together We Shine, United We Soar!
Mei, J., Leung, N. L. C., Kwok, R. T. K., Lam, J. W. Y., & Tang, B. Z. (2015) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00263 · Cited by 8,270 · see citing works
Self-citationBarman, D., Narang, K., Parui, R., Zehra, N., Khatun, M. N., Adil, L. R., & Iyer, P. K. (2022) · Aggregate · doi:10.1002/agt2.172 · Cited by 113 · see citing works
- Authors
- Chan, C. Y. K., Lam, J. W. Y., Jim, C. K. W., Sung, H. H. Y., Williams, I. D., & Tang, B. Z.
- Affiliations
- Hong Kong University of Science and Technology (HK)
- Corresponding author
- Tang, Ben Zhong
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-12-02
- Volume
- 46
- Issue
- 24
- Pages
- 9494-9506
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2147786107
- Cited by
- 44
- References
- 86
- Citations by year
- 2025: 1 · 2024: 4 · 2023: 1 · 2022: 3 · 2021: 2 · 2020: 1 · 2019: 5 · 2018: 4 · 2017: 2 · 2016: 4 · 2015: 9 · 2014: 7 · 2012: 1
- FWCI
- 4.81
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Rare & Special e-Zone (The Hong Kong University of Science and Technology) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Dendrimers and Hyperbranched Polymers
- Physical Sciences › Materials Science › Polymers and Plastics › Synthesis and properties of polymers
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- polycyclotrimerization, dinitriles, hyperbranched polymers, nitrogen-rich polymers, degree of branching, refractive index, optical dispersion, Abbe number, optical transparency, tetraphenylethylene, aggregation-induced emission, fluorescent sensors, thermally stable polymers
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
