Dual-Mediated Aggregate Electrochemiluminescence of Rubrene

Li Dai , Tong Jiang , Baotao Kang , Yu Du , Zhongfeng Gao , Xiang Ren , Dan Wu , Hongmin Ma , Qin Wei , Huangxian Ju

Aggregate ›› 2026, Vol. 7 ›› Issue (3) : e70315

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Aggregate ›› 2026, Vol. 7 ›› Issue (3) :e70315 DOI: 10.1002/agt2.70315
RESEARCH ARTICLE
Dual-Mediated Aggregate Electrochemiluminescence of Rubrene
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Abstract

Electrochemiluminescence (ECL) populates the luminescent excited states through electrochemical reactions. It is challenging to mediate the ECL behaviors of molecular nanoaggregates because both the photophysical and electrochemical properties usually deteriorate in aggregate states. In this work, we demonstrate an unprecedented supramolecular strategy that simultaneously modulates both the photophysical and electrochemical factors governing ECL. The ECL performance of rubrene (RUB) nanoaggregates can be significantly enhanced through the incorporation of hole-transporting molecules as both redox and photophysical mediators. A balanced state, inhibiting the singlet fission (SF) and retaining the triplet-triplet annihilation (TTA), was achieved for RUB, which not only reduced the quenching of luminescent singlet state excitons but also well utilized the electrochemically generated triplet state excitons. The redox-mediating properties of hole-transporting molecules toward co-reactant not only promote the formation of excitons but also reduce the luminescent potential. The RUB nanoaggregates showed significantly enhanced photoluminescence quantum efficiency (2.3-fold) and ECL intensity (50-fold) in aqueous conditions and were demonstrated as promising ECL imaging probes. This work opens up a new avenue for the preparation of ECL nano-emitters with high-brightness in aqueous conditions.

Keywords

electrochemiluminescence / hole-transporting / microfluidic chips / nanoaggregates

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Li Dai, Tong Jiang, Baotao Kang, Yu Du, Zhongfeng Gao, Xiang Ren, Dan Wu, Hongmin Ma, Qin Wei, Huangxian Ju. Dual-Mediated Aggregate Electrochemiluminescence of Rubrene. Aggregate, 2026, 7 (3) : e70315 DOI:10.1002/agt2.70315

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References

[1]

Y. Wang, J. Ding, P. Zhou, et al., “Electrochemiluminescence Distance and Reactivity of Coreactants Determine the Sensitivity of Bead-Based Immunoassays,” Angewandte Chemie International Edition 62 (2023): e202216525.

[2]

J. Dong, Y. Lu, Y. Xu, et al., “Direct Imaging of Single-Molecule Electrochemical Reactions in Solution,” Nature 596 (2021): 244-249.

[3]

S. Knezevic, D. Han, B. Liu, D. Jiang, and N. Sojic, “Electrochemiluminescence Microscopy,” Angewandte Chemie International Edition 63 (2024): e202407588.

[4]

Y. Zhao, L. Bouffier, G. Xu, G. Loget, and N. Sojic, “Electrochemiluminescence With Semiconductor Nanomaterials,” Chemical Science 13 (2022): 2528-2550.

[5]

S. O'Connor, L. Dennany, and E. O'Reilly, “Evolution of Nanomaterial Electrochemiluminescence Luminophores Towards Biocompatible Materials,” Biosensors & Bioelectronics 149 (2023): 108286.

[6]

R. Luo, H. Lv, Q. Liao, et al., “Intrareticular Charge Transfer Regulated Electrochemiluminescence of Donor-Acceptor Covalent Organic Frameworks,” Nature Communications 12 (2021): 6808.

[7]

B. Yin, L. Jiang, X. Wang, et al., “Bright Dual-Color Electrochemiluminescence of a Structurally Determined Pt1Ag18 Nanocluster,” Aggregate 5 (2024): e417.

[8]

E. Kerr, S. Knezevic, P. S. Francis, et al., “Electrochemiluminescence Amplification in Bead-Based Assays Induced by a Freely Diffusing Iridium(III) Complex,” ACS Sensors 8 (2023): 933-939.

[9]

M. Liu, X. Huang, B. Goudeau, C. Wang, N. Sojic, and H. Li, “Electrochemiluminescence Modulation by a Versatile Organic Redox Mediator,” Angewandte Chemie International Edition 64 (2025): e20178.

[10]

W. Miao, “Electrogenerated Chemiluminescence and Its Biorelated Applications,” Chemical Reviews 108 (2008): 2506-2553.

[11]

K. Chu, Z. Ding, and E. Zysman-Colman, “Materials for Electrochemiluminescence: TADF, Hydrogen-Bonding, and Aggregation- and Crystallization-Induced Emission Luminophores,” Chemistry - A European Journal 29 (2023): e202301504.

[12]

R. Ishimatsu, S. Matsunami, T. Kasahara, et al., “Electrogenerated Chemiluminescence of Donor-Acceptor Molecules With Thermally Activated Delayed Fluorescence,” Angewandte Chemie International Edition 53 (2014): 6993-6996.

[13]

E. M. Gross, N. R. Armstrong, and R. M. Wightman, “Electrogenerated Chemiluminescence From Phosphorescent Molecules Used in Organic Light-Emitting Diodes,” Journal of the Electrochemical Society 149 (2002): E137-E142.

[14]

B. Zhang, Y. Kong, H. Liu, et al., “Aggregation-Induced Delayed Fluorescence Luminogens: The Innovation of Purely Organic Emitters for Aqueous Electrochemiluminescence,” Chemical Science 12 (2021): 13283-13291.

[15]

H. Gao, S. Y. Shi, S. M. Wang, et al., “Aggregation-Induced Delayed Electrochemiluminescence of Organic Dots in Aqueous Media,” Aggregate 5 (2024): e394.

[16]

R. Ishimatsu, Y. Kirino, C. Adachi, K. Nakano, and T. Imato, “Quenching Behavior of Thermally Activated Delayed Fluorescence From a Donor-Acceptor Molecule, 1,2,3,5-Tetrakis(Carbazol-9-yl)-4,6-Dicyanobenzene by O2,” Chemistry Letters 45 (2016): 1183-1185.

[17]

L. Huang, T. Le, K. Huang, and G. Han, “Enzymatic Enhancing of Triplet-Triplet Annihilation Upconversion by Breaking Oxygen Quenching for Background-Free Biological Sensing,” Nature Communications 12 (2021): 1898.

[18]

D. Di, L. Yang, J. M. Richter, et al., “Efficient Triplet Exciton Fusion in Molecularly Doped Polymer Light-Emitting Diodes,” Advanced Materials 29 (2017): 1605987.

[19]

E. Radiunas, L. Naimovičius, P. Baronas, A. Jozeliūnaitė, E. Orentas, and K. Kazlauskas, “CN-Tuning: A Pathway to Suppress Singlet Fission and Amplify Triplet-Triplet Annihilation Upconversion in Rubrene,” Advanced Optical Materials 13 (2025): 12.

[20]

J. T. Maloy and A. J. Bard, “Electrogenerated Chemiluminescence. VI. Studies of the Efficiency and Mechanisms of 9,10-Diphenylanthracene, Rubrene, and Pyrene Systems at a Rotating-Ring-Disk Electrode,” Journal of the American Chemical Society 93 (1971): 5968-5981.

[21]

K. M. Omer and A. J. Bard, “Electrogenerated Chemiluminescence of Aromatic Hydrocarbon Nanoparticles in an Aqueous Solution,” Journal of Physical Chemistry C 113 (2009): 11575-11578.

[22]

L. Dai, J. Fang, T. Jiang, et al., “Multicomponent Supramolecular Nanoaggregates With Co-Emissive Electrochemiluminescence,” Matter 8 (2025): 102056.

[23]

N. S. Adamson, S. J. Blom, E. H. Doeven, et al., “Electrochemiluminescence Enhanced by a Non-Emissive Dual Redox Mediator,” Angewandte Chemie International Edition 63 (2024): e202412097.

[24]

P.-H. Sher, C.-H. Chen, T.-L. Chiu, C.-F. Lin, J.-K. Wang, and J.-H. Lee, “Distinct Routes of Singlet Fission and Triplet Fusion: A Fluorescence Kinetic Study of Rubrene,” Journal of Physical Chemistry C 123 (2019): 3279-3284.

[25]

E. Radiunas, M. Dapkevicius, S. Raisys, et al., “Impact of t-Butyl Substitution in a Rubrene Emitter for Solid State NIR-to-Visible Photon Upconversion,” Physical Chemistry Chemical Physics 22 (2020): 7392-7403.

[26]

E. Radiunas, M. Dapkevicius, S. Raisys, and K. Kazlauskas, “Triplet and Singlet Exciton Diffusion in Disordered Rubrene Films: Implications for Photon Upconversion,” Physical Chemistry Chemical Physics 24 (2022): 24345-24352.

[27]

P. Baronas, G. Kreiza, L. Naimovicius, et al., “Sweet Spot of Intermolecular Coupling in Crystalline Rubrene: Intermolecular Separation to Minimize Singlet Fission and Retain Triplet-Triplet Annihilation,” Journal of Physical Chemistry C 126 (2022): 15327-15335.

[28]

W. Jia, Q. Chen, L. Chen, et al., “Molecular Spacing Modulated Conversion of Singlet Fission to Triplet Fusion in Rubrene-Based Organic Light-Emitting Diodes at Ambient Temperature,” Journal of Physical Chemistry C 120 (2016): 8380-8386.

[29]

X. Tian, L. Zhou, X. Chen, et al., “Nanoscale Exponential Distance Dependence and Electron-Transfer Model for Intermolecular Singlet Exciton Fission Observed in Rubrene-Doped Organic Films,” Organic Electronics 50 (2017): 429-434.

[30]

J. E. Dick, C. Renault, B. K. Kim, and A. J. Bard, “Electrogenerated Chemiluminescence of Common Organic Luminophores in Water Using an Emulsion System,” Journal of the American Chemical Society 136 (2014): 13546-13549.

[31]

S. Knežević, E. Kerr, G. Valenti, et al., “Electrocatalytic Amplification of Coreactant Electrochemiluminescence Using Redox Mediators,” Electrochimica Acta 499 (2024): 144677.

[32]

R. Y. Lai and A. J. Bard, “Electrogenerated Chemiluminescence. 70. The Application of ECL to Determine Electrode Potentials of Tri-n-Propylamine, Its Radical Cation, and Intermediate Free Radical in MeCN/Benzene Solutions,” Journal of Physical Chemistry A 107 (2003): 3335-3340.

[33]

E. Kerr, D. J. Hayne, L. C. Soulsby, et al., “A Redox-Mediator Pathway for Enhanced Multi-Colour Electrochemiluminescence in Aqueous Solution,” Chemical Science 13 (2022): 469-477.

[34]

A. Fracassa, C. I. Santo, E. Kerr, et al., “Redox-Mediated Electrochemiluminescence Enhancement for Bead-Based Immunoassay,” Chemical Science 15 (2024): 1150-1158.

[35]

P. J. Low, M. A. J. Paterson, A. E. Goeta, et al., “The Molecular Structures and Electrochemical Response of “Twisted” Tetra(Aryl)Benzidenes,” Journal of Materials Chemistry 14 (2004): 2516-2523.

[36]

F. Kanoufi and A. J. Bard, “Electrogenerated Chemiluminescence. 65. An Investigation of the Oxidation of Oxalate by Tris(Polypyridine) Ruthenium Complexes and the Effect of the Electrochemical Steps on the Emission Intensity,” Journal of Physical Chemistry B 103 (1999): 10469-10480.

[37]

G. R. Hutchison, M. A. Ratner, and T. J. Marks, “Hopping Transport in Conductive Heterocyclic Oligomers: Reorganization Energies and Substituent Effects,” Journal of the American Chemical Society 127 (2005): 2339-2350.

[38]

D. P. McMahon and A. Troisi, “Evaluation of the External Reorganization Energy of Polyacenes,” Journal of Physical Chemistry Letters 1 (2010): 941-946.

[39]

S. Luo, B. Zheng, and S. Dong, “Natural Light-Regulated Switchable Self-Adhesive Supramolecular Films for Smart Windows,” Chemistry - A European Journal 29 (2023): e202301277.

[40]

L.-F. Ji, J.-X. Fan, G.-Y. Qin, N.-X. Zhang, P.-P. Lin, and A.-M. Ren, “Theoretical Study on the Electronic Structures and Charge Transport Properties of a Series of Rubrene Derivatives,” Journal of Physical Chemistry C 122 (2018): 21226-21238.

[41]

R. Herzhoff, F. Negri, K. Meerholz, and D. Fazzi, “Revealing the Interplay Between the Structural Complexity of Triphenylamine Redox Derivatives and Their Charge Transport Processes via Computational Modeling,” Journal of Materials Chemistry C 11 (2023): 11969-11979.

[42]

V. Vaissier, P. Barnes, J. Kirkpatrick, and J. Nelson, “Influence of Polar Medium on the Reorganization Energy of Charge Transfer Between Dyes in a Dye Sensitized Film,” Physical Chemistry Chemical Physics 15 (2013): 4804-4814.

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2026 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.

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