AIE-active Metal-organic Coordination Complexes Based on Tetraphenylethylene Unit and Their Applications

  • Bo Jiang
  • Chang-Wei Zhang
  • Xue-Liang ShiEmail author
  • Hai-Bo Yang


Tetraphenylethylene (TPE) and its derivatives, as the widely used aggregation-induced emission (AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks (MOFs).


Aggregation-induced emission Self-assembly Metal-organic coordination complexes Tetraphenylethylene Sensor 


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This work was financially supported by STCSM (No. 16XD 1401000) and Program for Changjiang Scholars and Innovative Research Team in University.


  1. 1.
    Datta, S.; Saha, M. L.; Stang, P. J. Hierarchical assemblies of supramolecular coordination complexes. Acc. Chem. Res. 2018, 51, 2047–2063.CrossRefGoogle Scholar
  2. 2.
    Cook, T. R.; Stang, P. J. Recent developments in the preparation and chemistry of metallacycles and metallacages via coordination. Chem. Rev. 2015, 115, 7001–7045.CrossRefGoogle Scholar
  3. 3.
    Cook, T. R.; Zheng, Y. R.; Stang, P. J. Metal-organic frameworks and self-assembled supramolecular coordination complexes: Comparing and contrasting the design, synthesis, and functionality of metal-organic materials. Chem. Rev. 2013, 113, 734–777.CrossRefGoogle Scholar
  4. 4.
    Chen, L. J.; Yang, H. B. Construction of stimuli-responsive functional materials via hierarchical self-assembly involving coordination interactions. Acc. Chem. Res. 2018, 51, 2699–2710.CrossRefGoogle Scholar
  5. 5.
    Chen, L. J.; Yang, H. B.; Shionoya, M. Chiral metallosupramolecular architectures. Chem. Soc. Rev. 2017, 46, 2555–2576.CrossRefGoogle Scholar
  6. 6.
    Wang, W.; Wang, Y. X.; Yang, H. B. Supramolecular transformations within discrete coordination-driven supramolecular architectures. Chem. Soc. Rev. 2016, 45, 2656–2693.CrossRefGoogle Scholar
  7. 7.
    Xu, L.; Wang, Y. X.; Chen, L. J.; Yang, H. B. Construction of multiferrocenyl metallacycles and metallacages via coordination- driven self-assembly: From structure to functions. Chem. Soc. Rev. 2015, 44, 2148–2167.CrossRefGoogle Scholar
  8. 8.
    Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Coordination assemblies from a Pd(II)-cornered square complex. Acc. Chem. Res. 2005, 38, 369–378.CrossRefGoogle Scholar
  9. 9.
    Caulder, D. L.; Raymond, K. N. Supermolecules by design. Acc. Chem. Res. 1999, 32, 975–982.CrossRefGoogle Scholar
  10. 10.
    Oliveri, C. G.; Ulmann, P. A.; Wiester, M. J.; Mirkin, C. A. Heteroligated supramolecular coordination complexes formed via the halide-induced ligand rearrangement reaction. Acc. Chem. Res. 2008, 41, 1618–1629.CrossRefGoogle Scholar
  11. 11.
    Eryazici, I.; Moorefield, C. N.; Newkome, G. R. Square-planar Pd(II), Pt(II), and Au(III) terpyridine complexes: Their syntheses, physical properties, supramolecular constructs, and biomedical activities. Chem. Rev. 2008, 108, 1834–1895.CrossRefGoogle Scholar
  12. 12.
    Nitschke, J. R. Construction, substitution, and sorting of metallo-organic structures via subcomponent self-assembly. Acc. Chem. Res. 2007, 40, 103–112.CrossRefGoogle Scholar
  13. 13.
    Han, Y. F.; Jin, G. X. Half-sandwich iridium- and rhodiumbased organometallic architectures: Rational design, synthesis, characterization, and applications. Acc. Chem. Res. 2014, 47, 3571–3579.CrossRefGoogle Scholar
  14. 14.
    Clever, G. H.; Punt, P. Cation-anion arrangement patterns in self-assembled Pd2L4 and Pd4L8 coordination cages. Acc. Chem. Res. 2017, 50, 2233–2243.CrossRefGoogle Scholar
  15. 15.
    Mukherjee, S.; Mukherjee, P. S. Versatility of azide in serendipitous assembly of copper(II) magnetic polyclusters. Acc. Chem. Res. 2013, 46, 2556–2566.CrossRefGoogle Scholar
  16. 16.
    Yan, X.; Li, S.; Cook, T. R.; Ji, X.; Yao, Y.; Pollock, J. B.; Shi, Y.; Yu, G.; Li, J.; Huang, F.; Stang, P. J. Hierarchical self-assembly: Well-defined supramolecular nanostructures and metallohydrogels via amphiphilic discrete organoplatinum(II) metallacycles. J. Am. Chem. Soc. 2013, 135, 14036–14039.CrossRefGoogle Scholar
  17. 17.
    Pollock, J. B.; Schneider, G. L.; Cook, T. R.; Davies, A. S.; Stang, P. J. Tunable visible light emission of self-assembled rhomboidal metallacycles. J. Am. Chem. Soc. 2013, 135, 13676–13679.CrossRefGoogle Scholar
  18. 18.
    Yan, X.; Cook, T. R.; Pollock, J. B.; Wei, P.; Zhang, Y.; Yu, Y.; Huang, F.; Stang, P. J. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven selfassembly and host/guest interactions. J. Am. Chem. Soc. 2014, 136, 4460–4463.CrossRefGoogle Scholar
  19. 19.
    Neti, V. S. P. K.; Saha, M. L.; Yan, X.; Zhou, Z.; Stang, P. J. Coordination-driven self-assembly of fullerene-functionalized Pt(II) metallacycles. Organometallics 2015, 34, 4813–4815.CrossRefGoogle Scholar
  20. 20.
    Chen, L. J.; Zhao, G. Z.; Jiang, B.; Sun, B.; Wang, M.; Xu, L.; He, J.; Abliz, Z.; Tan, H.; Li, X.; Yang, H. B. Smart stimuli-re-sponsive spherical nanostructures constructed from supramolecular metallodendrimers via hierarchical self-assembly. J. Am. Chem. Soc. 2014, 136, 5993–6001.CrossRefGoogle Scholar
  21. 21.
    Chen, L. J.; Jiang, B.; Yang, H. B. Transformable nanostructures of cholesteryl-containing rhomboidal metallacycles through hierarchical self-assembly. Org. Chem. Front. 2016, 3, 579–587.CrossRefGoogle Scholar
  22. 22.
    Li, Z. Y.; Zhang, Y.; Zhang, C. W.; Chen, L. J.; Wang, C.; Tan, H.; Yu, Y.; Li, X.; Yang, H. B. Cross-linked supramolecular polymer gels constructed from discrete multi-pillar[5]arene metallacycles and their multiple stimuli-responsive behavior. J. Am. Chem. Soc. 2014, 136, 8577–8589.CrossRefGoogle Scholar
  23. 23.
    Jiang, B.; Zhang, J.; Ma, J.; Zheng, W.; Chen, L. J.; Sun, B.; Li, C.; Hu, B.; Tan, H.; Li, X.; Yang, H. B. Vapochromic behavior of a chair-shaped supramolecular metallacycle with ultra-stability. J. Am. Chem. Soc. 2016, 138, 738–741.CrossRefGoogle Scholar
  24. 24.
    Jiang, B.; Chen, L. J.; Zhang, Y.; Tan, H.; Xu, L.; Yang, H. B. Hierarchical self-assembly of triangular metallodendrimers into the ordered nanostructures. Chin. Chem. Lett. 2016, 27, 607–612.CrossRefGoogle Scholar
  25. 25.
    Jiang, B.; Zhang, J.; Zheng, W.; Chen, L. J.; Yin, G. Q.; Wang, Y. X.; Sun, B.; Li, X.; Yang, H. B. Construction of alkynylplatinum( II) bzimpy-functionalized metallacycles and their hierarchical self-assembly behavior in solution promoted by Pt···Pt and π-π interactions. Chem. Eur. J. 2016, 22, 14664–14671.CrossRefGoogle Scholar
  26. 26.
    Zhang, Y.; Zhou, Q. F.; Huo, G.; Yin, G. Q.; Zhao, X.; Jiang, B.; Tan, H.; Li, X.; Yang, H. B. Hierarchical self-assembly of an alkynylplatinum(ll) bzimpy-functionalized metallacage via Pt···Pt and π-π Interactions. Inorg. Chem. 2018, 57, 3516–3520.CrossRefGoogle Scholar
  27. 27.
    Zhang, J.; Marega, R.; Chen, L. J.; Wu, N. W.; Xu, X. D.; Muddiman, D. C.; Bonifazi, D.; Yang, H. B. Hierarchical selfassembly of supramolecular hydrophobic metallacycles into ordered nanostructures. Chem. Asian J. 2014, 9, 2928–2936.CrossRefGoogle Scholar
  28. 28.
    Wu, N. W.; Chen, L. J.; Wang, C.; Ren, Y. Y.; Li, X.; Xu, L.; Yang, H. B. Hierarchical self-assembly of a discrete hexagonal metallacycle into the ordered nanofibers and stimuli-responsive supramolecular gels. Chem. Commun. 2014, 50, 4231–4233.CrossRefGoogle Scholar
  29. 29.
    Wang, W.; Zhang, Y.; Sun, B.; Chen, L. J.; Xu, X. D.; Wang, M.; Li, X.; Yu, Y.; Jiang, W.; Yang, H. B. The construction of complex multicomponent supramolecular systems via the combination of orthogonal self-assembly and the self-sorting approach. Chem. Sci. 2014, 5, 4554–4560.CrossRefGoogle Scholar
  30. 30.
    Zhao, G. Z.; Chen, L. J.; Wang, W.; Zhang, J.; Yang, G.; Wang, D. X.; Yu, Y.; Yang, H. B. Stimuli-responsive supramolecular gels through hierarchical self-assembly of discrete rhomboidal metallacycles. Chem. Eur. J. 2013, 19, 10094–10100.CrossRefGoogle Scholar
  31. 31.
    Wang, X. Q.; Wang, W.; Yin, G. Q.; Wang, Y. X.; Zhang, C. W.; Shi, J.; Yu, Y.; Yang, H. B. Cross-linked supramolecular polymer metallogels constructed via a self-sorting strategy and their multiple stimulus-response behaviors. Chem. Commun. 2015, 51, 16813–16816.CrossRefGoogle Scholar
  32. 32.
    McConnell, A. J.; Wood, C. S.; Neelakandan, P. P.; Nitschke, J. R. Stimuli-responsive metal-ligand assemblies. Chem. Rev. 2015, 115, 7729–7793.CrossRefGoogle Scholar
  33. 33.
    Luo, J.; Xie, Z.; Lam, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, D.; Tang, B. Z. Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. Chem. Commun. 2001, 1740–1741.Google Scholar
  34. 34.
    Mei, J.; Leung, N. L. C.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z. Aggregation-induced emission: Together we shine, united we soar! Chem. Rev. 2015, 115, 11718–11940.CrossRefGoogle Scholar
  35. 35.
    Ding, D.; Li, K.; Liu, B.; Tang, B. Z. Bioprobes based on AIE fluorogens. Acc. Chem. Res. 2013, 46, 2441–2453.CrossRefGoogle Scholar
  36. 36.
    Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Aggregation-induce emission. Chem. Soc. Rev. 2011, 40, 5361–5388.CrossRefGoogle Scholar
  37. 37.
    Feng, G.; Liu, B. Aggregation-induced emission (AIE) dots: Emerging theranostic nanolights. Acc. Chem. Res. 2018, 51, 1404–1414.CrossRefGoogle Scholar
  38. 38.
    Liu, Y.; Deng, C.; Tang, L.; Qin, A.; Hu, R.; Sun, J. Z.; Tang, B. Z. Specific detection of D-glucose by a tetraphenylethenebased fluorescent sensor. J. Am. Chem. Soc. 2011, 133, 660–663.CrossRefGoogle Scholar
  39. 39.
    Wang, J.; Mei, J.; Hu, R.; Sun, J. Z.; Qin, A.; Tang, B. Z. Click synthesis, aggregation-induced emission, E/Z isomerization, self-organization, and multiple chromisms of pure stereoisomers of a tetraphenylethene-cored luminogen. J. Am. Chem. Soc. 2012, 134, 9956–9966.CrossRefGoogle Scholar
  40. 40.
    Xu, S.; Yuan, Y.; Cai, X.; Zhang, C. J.; Hu, F.; Liang, J.; Zhang, G.; Zhang, D.; Liu, B. Tuning the singlet-triplet energy gap: A unique approach to efficient photosensitizers with aggregation- induced emission (AIE) characteristics. Chem. Sci. 2015, 6, 5824–5830.CrossRefGoogle Scholar
  41. 41.
    Zhang, C. W.; Ou, B.; Jiang, S. T.; Yin, G. Q.; Chen, L. J.; Xu, L.; Li, X.; Yang, H. B. Cross-linked AIE supramolecular polymer gels with multiple stimuli-responsive behaviours constructed by hierarchical self-assembly. Polym. Chem. 2018, 9, 2021–2030.CrossRefGoogle Scholar
  42. 42.
    Zhang, C. W.; Jiang, S. T.; Yin, G. Q.; Li, X.; Zhao, X. L.; Yang H. B. Dual stimuli-responsive cross-linker AIE supramolecular polymer constructed through hierarchical self-assembly. Isr. J. Chem. 2018.Google Scholar
  43. 43.
    Zheng, W.; Yang, G.; Jiang, S.; Shao, N.; Yin, G. Q.; Xu, L.; Li, X.; Chen, G.; Yang, H. B. A Tetraphenylethylene (TPE)- based supra-amphiphilic organoplatinum(II) metallacycle and its self-assembly behaviour. Mater. Chem. Front. 2017, 1, 1823–1828.CrossRefGoogle Scholar
  44. 44.
    Chen, L. J.; Ren, Y. Y.; Wu, N. W.; Sun, B.; Ma, J.; Zhang, L.; Tan, H.; Liu, M.; Li, X.; Yang, H. B. Hierarchical self-assembly of discrete organoplatinum(II) metallacycles with polysaccharide via electrostatic interactions and their application for heparin detection. J. Am. Chem. Soc. 2015, 137, 11725–11735.CrossRefGoogle Scholar
  45. 45.
    Yin, G. Q.; Wang, H.; Wag, X. Q.; Song, B.; Chen, L. J.; Wang, L.; Hao, X. Q.; Yang, H. B.; Li, X. Self-assembly of emissive supramolecular rosettes with increasing complexity using multitopic terpyridine ligands. Nat. Commun. 2018, 9, 567.CrossRefGoogle Scholar
  46. 46.
    Zhang, M.; Li, S.; Yan, X.; Zhou, Z.; Saha, M. L.; Wang, Y. C.; Stang, P. J. Fluorescent metallacycle-cored polymers via covalent linkage and their use as contrast agents for cell imaging. Proc. Natl. Acad. Sci. 2016, 113, 11100–11105.CrossRefGoogle Scholar
  47. 47.
    Yan, X.; Wang, H.; Hauke, C. E.; Cook, T. R.; Wang, M.; Saha, M. L.; Zhou, Z.; Zhang, M.; Li, X.; Huang, F.; Stang, P. J. A suite of tetraphenylethylene-based discrete organoplatinum( II) metallacycles: Controllable structure and stoichiometry, aggregation-induced emission, and nitroaromatics sensing. J. Am. Chem. Soc. 2015, 137, 15276–15286.CrossRefGoogle Scholar
  48. 48.
    Yan, X.; Wang, W.; Cook, T. R.; Zhang, M.; Saha, M. L.; Zhou, Z.; Li, X.; Huang, F.; Stang, P. J. Light-emitting superstructures with anion effect: Coordination-driven self-assembly of pure tetraphenylethylene metallacycles and metallacages. J. Am. Chem. Soc. 2016, 138, 4580–4588.CrossRefGoogle Scholar
  49. 49.
    Zhou, Z.; Yan, X.; Saha, M. L.; Zhang, M.; Wang, M.; Li, X.; Stang, P. J. Immobilizing tetraphenylethylene into fused metallacycles: Shape effects on fluorescence emission. J. Am. Chem. Soc. 2016, 138, 13131–13134.CrossRefGoogle Scholar
  50. 50.
    Tian, Y.; Yan, X.; Saha, M. L.; Niu, Z.; Stang, P. J. Hierarchical self-assembly of responsive organoplatinum(II) metallacycle- TMV complexes with turn-on fluorescence. J. Am. Chem. Soc. 2016, 138, 12033–12036.CrossRefGoogle Scholar
  51. 51.
    Yu, G.; Zhang, M.; Saha, M. L.; Mao, Z.; Chen, J.; Yao, Y.; Zhou, Z.; Liu, Y.; Gao, C.; Huang, F.; Chen, X.; Stang, P. J. Antitumor activity of a unique polymer that incorporates a fluorescent self-assembled metallacycle. J. Am. Chem. Soc. 2017, 139, 15940–15949.CrossRefGoogle Scholar
  52. 52.
    Yan, X.; Cook, T. R.; Wang, P.; Huang, F.; Stang, P. J. Highly emissive platinum(II) metallacages. Nat. Chem. 2015, 7, 342–348.CrossRefGoogle Scholar
  53. 53.
    Zhang, M.; Saha, M. L.; Wang, M.; Zhou, Z.; Song, B.; Lu, C.; Yan, X.; Li, X.; Huang, F.; Yin, S.; Stang, P. J. Multicomponent platinum(II) cages with tunable emission and amino acid sensing. J. Am. Chem. Soc. 2017, 139, 5067–5074.CrossRefGoogle Scholar
  54. 54.
    Lu, C.; Zhang, M.; Tang, D.; Yan, X.; Zhang, Z.; Zhou, Z.; Song, B.; Wang, H.; Li, X.; Yin, S.; Sepehrpour, H.; Stang, P. J. Fluorescent metallacage-core supramolecular polymer gel formed by orthogonal metal coordination and host-guest interactions. J. Am. Chem. Soc. 2018, 140, 7674–7680.CrossRefGoogle Scholar
  55. 55.
    Sun, Y.; Yao, Y.; Wang, H.; Fu, W.; Chen, C.; Saha, M. L.; Zhang, M.; Datta, S.; Zhou, Z.; Yu, H.; Li, X.; Stang, P. J. Selfassembly of metallacages into multidimensional suprastructures with tunable emissions. J. Am. Chem. Soc. 2018, 140, 12819–12828.CrossRefGoogle Scholar
  56. 56.
    Yu, G.; Cook, T. R.; Li, Y.; Yan, X.; Wu, D.; Shao, L.; Shen, J.; Tang, G.; Huang, F.; Chen, X.; Stang, P. J. Tetraphenylethene- based highly emissive metallacage as a component of theranostic supramolecular nanoparticles. Proc. Natl. Acad. Sci. 2016, 113, 13720–13725.CrossRefGoogle Scholar
  57. 57.
    Shustova, N. B.; McCarthy, B. D.; Dinca, M. Turn-on in tetraphenylethylene- based metal-organic frameworks: An alternative to aggregation-induced emission. J. Am. Chem. Soc. 2011, 133, 20126–20129.CrossRefGoogle Scholar
  58. 58.
    Shustova, N. B.; Cozzoline, A. F.; Reineke, S.; Baldo, M.; Dinca, M. Selective turn-on ammonia sensing enabled by hightemperature fluorescence in metal-organic frameworks with open metal sites. J. Am. Chem. Soc. 2013, 135, 13326–13329.CrossRefGoogle Scholar
  59. 59.
    Shustova, N.; Cozzolino, A. F.; Dinca, M. Conformational locking by design: Relating strain energy with luminescence and stability in rigid metal-organic frameworks. J. Am. Chem. Soc. 2012, 134, 19596–19599.CrossRefGoogle Scholar
  60. 60.
    Shustova, N. B.; Ong, T.; Cozzolino, A. F.; Michaelis, V. K.; Griffin, R. G.; Dinca, M. Phenyl ring dynamics in a tetraphenylethylene- bridged metal-organic framework: Implications for the mechanism of aggregation induced emission. J. Am. Chem. Soc. 2012, 134, 15061–15070.CrossRefGoogle Scholar
  61. 61.
    Zhang, Q.; Su, J.; Feng, D.; Wei, Z.; Zou, X.; Zhou, H. C. Piezofluorochromic metal-organic framework: A microscissor lift. J. Am. Chem. Soc. 2015, 137, 10064–10067.CrossRefGoogle Scholar
  62. 62.
    Wei, Z.; Gu, Z. Y.; Arvapallu, R. K.; Chen, Y. P.; McDougald, Jr. R. N.; Ivy, J. F.; Yakovenko, A. A.; Feng, D.; Omary, M. A.; Zhou, H. C. Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement. J. Am. Chem. Soc. 2014, 136, 8269–8276.CrossRefGoogle Scholar
  63. 63.
    Zhang, M.; Feng, G.; Song, Z.; Zhou, Y. P.; Chao, H. Y.; Yuan, D.; Tan, T. T. Y.; Guo, Z.; Hu, Z.; Tang, B. Z.; Liu, B.; Zhao, D. Two-dimensional metal-organic framework with wide channels and responsive turn-on fluorescence for the chemical sensing of volatile organic compounds. J. Am. Chem. Soc. 2014, 136, 7241–7244.CrossRefGoogle Scholar
  64. 64.
    Hu, Z.; Lustig, W. P.; Zhang, J.; Zheng, C.; Wang, H.; Teat, S. J.; Gong, Q.; Rudd, N. D.; Li, J. Effective detection of mycotoxins by a highly luminescent metal-organic framework. J. Am. Chem. Soc. 2015, 137, 16209–16215.CrossRefGoogle Scholar

Copyright information

© Chinese Chemical Society, Institute of Chemistry (CAS) and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Bo Jiang
    • 1
  • Chang-Wei Zhang
    • 1
  • Xue-Liang Shi
    • 1
    Email author
  • Hai-Bo Yang
    • 1
  1. 1.Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular EngineeringEast China Normal UniversityShanghaiChina

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