Cyanine dyes, despite their strong near-infrared (NIR) absorption, often undergo symmetry-breaking Peierls’ transitions in water known as the “cyanine limit,” resulting in suboptimal optical properties. In this work, we present a strategy to overcome this limitation by entrapping cyanine dye (Cy746) within the micellar nanoparticle (Np@M1-Cy746) of a bichromophoric [1+1] macrocycle M1 comprising of perylene diimide (PDI) and aza-BODIPY (Aza) that exhibits Förster resonance energy transfer (FRET), formed from an amphiphilic polymer 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)]. This approach not only stabilizes the cyanine dye but also enables two-step FRET from PDI to Aza of the macrocycle to Cy746, resulting in panchromatic absorption, enhanced NIR emission, and achieved near-white light emission. The micellar FRET assembly Np@M1-Cy746 also serves as a ratiometric temperature sensor with a sensitivity of 0.0379%°C−1 and was utilized as a supramolecular photocatalyst in aqueous-phase photocatalytic Knoevenagel condensation of benzaldehyde and malononitrile. The two-step FRET process in Np@M1-Cy746 enabled its superior photocatalytic performance compared to the micelle of only M1 (Np@M1), which shows one-step FRET. This study offers a distinct approach for constructing multichromophoric macrocycle nanoparticles in aqueous media, leveraging upon its sequential energy transfer to achieve efficient and scalable photocatalytic transformation.
| [1] |
H. Zhou and T. Ren, “Recent Progress of Cyanine Fluorophores for NIR-II Sensing and Imaging,” Chemistry—An Asian Journal 17 (2022): e202200147.
|
| [2] |
W. Sun, S. Guo, C. Hu, J. Fan, and X. Peng, “Recent Development of Chemosensors Based on Cyanine Platforms,” Chemical Reviews 116 (2016): 7768–7817.
|
| [3] |
J. Wu, Z. Shi, L. Zhu, et al., “The Design and Bioimaging Applications of NIR Fluorescent Organic Dyes With High Brightness,” Advanced Optical Materials 10 (2022): 2102514.
|
| [4] |
H. A. Shindy, “Fundamentals in the Chemistry of Cyanine Dyes: A Review,” Dyes and Pigments 145 (2017): 505–513.
|
| [5] |
X. Luo, J. Li, J. Zhao, L. Gu, X. Qian, and Y. Yang, “A General Approach to the Design of High-performance near-infrared (NIR) D-π-A Type Fluorescent Dyes,” Chinese Chemistry Letters 30 (2019): 839–846.
|
| [6] |
S. Luo, E. Zhang, Y. Su, T. Cheng, and C. Shi, “A Review of NIR Dyes in Cancer Targeting and Imaging,” Biomaterials 32 (2011): 7127–7138.
|
| [7] |
P. Chinna Ayya Swamy, G. Sivaraman, R. N. Priyanka, et al., “Near Infrared (NIR) Absorbing Dyes as Promising Photosensitizer for Photo Dynamic Therapy,” Coordination Chemistry Reviews 411 (2020): 213233.
|
| [8] |
J. O. Escobedo, O. Rusin, S. Lim, and R. M. Strongin, “NIR Dyes for Bioimaging Applications,” Current Opinion in Chemical Biology 14 (2010): 64–70.
|
| [9] |
S. Zhu, R. Tian, A. L. Antaris, X. Chen, and H. Dai, “Near-Infrared-II Molecular Dyes for Cancer Imaging and Surgery,” Advanced Materials 31 (2019): 1900321.
|
| [10] |
D. Ma, H. Bian, M. Gu, L. Wang, X. Chen, and X. Peng, “Recent Advances in the Design and Applications of near-infrared II Responsive Small Molecule Phototherapeutic Agents,” Coordination Chemistry Reviews 505 (2024): 215677.
|
| [11] |
F. Würthner, T. E. Kaiser, and C. R. Saha-Möller, “J-Aggregates: From Serendipitous Discovery to Supramolecular Engineering of Functional Dye Materials,” Angewandte Chemie International Edition 50 (2011): 3376–3410.
|
| [12] |
X. Huang, M. Gao, H. Xing, et al., “Rationally Designed Heptamethine Cyanine Photosensitizers that Amplify Tumor-Specific Endoplasmic Reticulum Stress and Boost Antitumor Immunity,” Small 18 (2022): 202202728.
|
| [13] |
C. G. Alves, R. Lima-Sousa, B. L. Melo, A. F. Moreira, I. J. Correia, and D. de Melo-Diogo, “Heptamethine Cyanine-Loaded Nanomaterials for Cancer Immuno-Photothermal/Photodynamic Therapy: A Review,” Pharmaceutics 14 (2022): 1015.
|
| [14] |
L. Wang, H. Fu, J. Lin, et al., “Harnessing the Biological Responses Induced by Nanomaterials for Enhanced Cancer Therapy,” Aggregate 6 (2025): e70080.
|
| [15] |
J. Lin, X. Cai, F. Zou, et al., “Fluorescent Nanoparticles Achieve Efficient Photothermal Conversion and Enhanced Antitumor Efficacy through Intermolecular Aggregation-Caused Quenching,” Aggregate 6 (2025): e723.
|
| [16] |
C. Shi, J. B. Wu, and D. Pan, “Review on near-infrared Heptamethine Cyanine Dyes as Theranostic Agents for Tumor Imaging, Targeting, and Photodynamic Therapy,” Journal of Biomedical Optics 21 (2016): 050901.
|
| [17] |
A. P. Gorka, R. R. Nani, and M. J. Schnermann, “Harnessing Cyanine Reactivity for Optical Imaging and Drug Delivery,” Accounts of Chemical Research 51 (2018): 3226–3235.
|
| [18] |
E. N. Bifari, P. Almeida, and R. M. El-Shishtawy, “Advancing Panchromatic Effect for Efficient Sensitization of Cyanine and Hemicyanine-based Dye-sensitized Solar Cells,” Materials Today Energy 36 (2023): 101337.
|
| [19] |
G. S. Gopika, P. M. H. Prasad, A. G. Lekshmi, et al., “Chemistry of Cyanine Dyes-A Review,” Materials Today Proceedings 46 (2021): 3102–3108.
|
| [20] |
N. Sellet, J. Frey, M. Cormier, and J.-P. Goddard, “Near-infrared Photocatalysis With Cyanines: Synthesis, Applications and Perspectives,” Chemical Science 15 (2024): 8639–8650.
|
| [21] |
N. Sellet, M. Cormier, and J.-P. Goddard, “The Dark Side of Photocatalysis: Near-infrared Photoredox Catalysis for Organic Synthesis,” Organic Chemistry Frontiers 8 (2021): 6783–6790.
|
| [22] |
A. Mishra, R. K. Behera, P. K. Behera, B. K. Mishra, and G. B. Behera, “Cyanines During the 1990s: a Review,” Chemical Reviews 100 (2000): 1973–2012.
|
| [23] |
P.-A. Bouit, C. Aronica, L. Toupet, B. Le Guennic, C. Andraud, and O. Maury, “Continuous Symmetry Breaking Induced by Ion Pairing Effect in Heptamethine Cyanine Dyes: Beyond the Cyanine Limit,” Journal of the American Chemical Society 132 (2010): 4328–4335.
|
| [24] |
W. Xu, E. Leary, S. Sangtarash, et al., “A Peierls Transition in Long Polymethine Molecular Wires: Evolution of Molecular Geometry and Single-Molecule Conductance,” Journal of the American Chemical Society 143 (2021): 20472–20481.
|
| [25] |
L. M. Tolbert and X. Zhao, “Beyond the Cyanine Limit: Peierls Distortion and Symmetry Collapse in a Polymethine Dye,” Journal of the American Chemical Society 119 (1997): 3253–3258.
|
| [26] |
D.-H. Li and B. D. Smith, “Supramolecular Mitigation of the Cyanine Limit Problem,” Journal of Organic Chemistry 87 (2022): 5893–5903.
|
| [27] |
X. Wu and W. Zhu, “Stability Enhancement of Fluorophores for Lighting up Practical Application in Bioimaging,” Chemical Society Reviews 44 (2015): 4179–4184.
|
| [28] |
Z. Tao, G. Hong, C. Shinji, et al., “Biological Imaging Using Nanoparticles of Small Organic Molecules With Fluorescence Emission at Wavelengths Longer Than 1000 Nm,” Angewandte Chemie International Edition 52 (2013): 13002–13006.
|
| [29] |
D. Gao, Z. Luo, Y. He, et al., “Low Dose NIR-II Preclinical Bioimaging Using Liposome-Encapsulated Cyanine Dyes,” Small 19 (2023): e202206544.
|
| [30] |
V. Gupta and S. Sengupta, “Advances in Multichromophoric Metal-Free FRET Macrocycles and 2D Metallacycles,” Chemistry—An Asian Journal 20 (2025): e00363.
|
| [31] |
H. S. Muddana, S. Sengupta, A. Sen, and P. J. Butler, “Enhanced Brightness and Photostability of Cyanine Dyes by Supramolecular Containment,” arXiv (2014): 1–20.
|
| [32] |
S. S. R. Kommidi and B. D. Smith, “Cucurbit[7]Uril Complexation of Near-Infrared Fluorescent Azobenzene-Cyanine Conjugates,” Molecules 27 (2022): 5440.
|
| [33] |
G. Soavi, A. Pedrini, A. Devi Das, et al., “Encapsulation of Trimethine Cyanine in Cucurbit[8]uril: Solution versus Solid-State Inclusion Behavior,” Chemistry—A European Journal 28 (2022): e202200185.
|
| [34] |
C. M. S. Yau, S. I. Pascu, S. A. Odom, et al., “Stabilisation of a Heptamethine Cyanine Dye by Rotaxane Encapsulation,” Chemical Communications (2008): 2897–2899.
|
| [35] |
J. Pruchyathamkorn, W. J. Kendrick, A. T. Frawley, et al., “A Complex Comprising a Cyanine Dye Rotaxane and a Porphyrin Nanoring as a Model Light-Harvesting System,” Angewandte Chemie International Edition 59 (2020): 16455–16458.
|
| [36] |
H. Zhang, Y. Masui, H. Masai, and J. Terao, “Post-Synthetic Modification of Near-Infrared Absorbing Cyclodextrin Encapsulated Cyanine Dyes for Controlling Absorption Wavelength, Stability and Singlet Oxygen Tolerance,” Bulletin of the Chemical Society of Japan 97 (2024): uoae055.
|
| [37] |
P.-P. Jia, Y.-X. Hu, Z.-Y. Peng, et al., “Construction of an Artificial Light-Harvesting System With Efficient Photocatalytic Activity in an Aqueous Solution Based on a FRET-Featuring Metallacage,” Inorganic Chemistry 62 (2023): 1950–1957.
|
| [38] |
R. Wang, H. Deng, W. Cheng, S. Li, W. Zhang, and Y. Ding, “Encapsulation of Solid-state Emissive Coumarins as Efficient FRET Energy Donors for Light-harvesting Applications,” Dyes and Pigments 235 (2025): 112578.
|
| [39] |
K. Rani and S. Sengupta, “Metal-free FRET Macrocycles of Perylenediimide and Aza-BODIPY for Multifunctional Sensing,” Chemical Communications 59 (2023): 1042–1045.
|
| [40] |
M. Eskandari, J. C. Roldao, J. Cerezo, B. Milián-Medina, and J. Gierschner, “Counterion-Mediated Crossing of the Cyanine Limit in Crystals and Fluid Solution: Bond Length Alternation and Spectral Broadening Unveiled by Quantum Chemistry,” Journal of the American Chemical Society 142 (2020): 2835–2843.
|
| [41] |
M. Karimi, P. Sahandi Zangabad, A. Ghasemi, et al., “Temperature-Responsive Smart Nanocarriers for Delivery of Therapeutic Agents: Applications and Recent Advances,” ACS Applied Materials and Interfaces 8 (2016): 21107–21133.
|
| [42] |
Z. Wang, X. He, T. Yong, Y. Miao, C. Zhang, and B. Z. Tang, “Multicolor Tunable Polymeric Nanoparticle From the Tetraphenylethylene Cage for Temperature Sensing in Living Cells,” Journal of the American Chemical Society 142 (2020): 512–519.
|
| [43] |
M. M. Ogle, A. D. Smith McWilliams, B. Jiang, and A. A. Martí, “Latest Trends in Temperature Sensing by Molecular Probes,” ChemPhotoChem 4 (2020): 255–270.
|
| [44] |
X. Wang, O. S. Wolfbeis, and R. J. Meier, “Luminescent Probes and Sensors for Temperature,” Chemical Society Reviews 42 (2013): 7834–7869.
|
| [45] |
X. Hu, Y. Li, T. Liu, G. Zhang, and S. Liu, “Intracellular Cascade FRET for Temperature Imaging of Living Cells With Polymeric Ratiometric Fluorescent Thermometers,” ACS Applied Materials and Interfaces 7 (2015): 15551–15560.
|
| [46] |
R. H. Vekariya and H. D. Patel, “Recent Advances in the Synthesis of Coumarin Derivatives via Knoevenagel Condensation: A Review,” Synthetic Communications 44 (2014): 2756–2788.
|
| [47] |
Z. Zhang, X. Nie, F. Wang, et al., “Rhodanine-based Knoevenagel Reaction and Ring-opening Polymerization for Efficiently Constructing Multicyclic Polymers,” Nature Communications 11 (2020): 3654.
|
| [48] |
A. R. Clapp, I. L. Medintz, and H. Mattoussi, “Förster Resonance Energy Transfer Investigations Using Quantum-Dot Fluorophores,” ChemPhysChem 7 (2006): 47–57.
|
| [49] |
D. Chen, T. Xiao, É. Monflier, and L. Wang, “Multi-step FRET Systems Based on Discrete Supramolecular Assemblies,” Communications Chemistry 7 (2024): 88.
|
| [50] |
A. Das and K. R. Justin Thomas, “Rose Bengal Photocatalyzed Knoevenagel Condensation of Aldehydes and Ketones in Aqueous Medium,” Green Chemistry 24 (2022): 4952–4957.
|
RIGHTS & PERMISSIONS
2025 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.
PDF
