The rational design of aqueous-phase supramolecular catalysts that integrate substrate recognition, activation, reaction selectivity, and recyclability remains a significant challenge. This work presents a cucurbit[8]uril (Q[8])-based supramolecular photocatalyst, TMV8+@Q[8], which selectively encapsulates aromatic sulfide substrates via host-stabilized charge transfer (HSCT) interactions while markedly enhancing singlet oxygen (1O2) generation. Under visible-light irradiation, the substrate-TMV8+@Q[8] system facilitates the efficient catalytic oxidation of aromatic sulfides to sulfoxides. Competitive displacement experiments confirm that product desorption is substrate-driven, enabling catalyst regeneration. Crucially, the Q[8] cavity plays a multifaceted role by enhancing substrate activation through HSCT, promoting 1O2-mediated oxidation via confinement effects, and enforcing selectivity through size exclusion. These findings establish a new paradigm for supramolecular photocatalysis, wherein macrocyclic confinement concurrently enhances substrate recognition, catalytic efficiency, and recyclability. This study thereby provides a strategic blueprint for designing enzyme-inspired supramolecular photocatalysts operable in aqueous media.
| [1] |
R. Buller, S. Lutz, R. J. Kazlauskas, R. Snajdrova, J. C. Moore, and U. T. Bornscheuer, “From Nature to Industry: Harnessing Enzymes for Biocatalysis,” Science 382 (2023): eadh8615.
|
| [2] |
D. Mondal, H. M. Snodgrass, C. A. Gomez, and J. C. Lewis, “Non-Native Site-Selective Enzyme Catalysis,” Chemical Reviews 123 (2023): 10381–10431.
|
| [3] |
J. Shi, Y. Wu, S. Zhang, Y. Tian, D. Yang, and Z. Jiang, “Bioinspired Construction of Multi-Enzyme Catalytic Systems,” Chemical Society Reviews 47 (2018): 4295–4313.
|
| [4] |
H. Gröger, F. Gallou, and B. H. Lipshutz, “Where Chemocatalysis Meets Biocatalysis: in Water,” Chemical Reviews 123 (2022): 5262–5296.
|
| [5] |
J. Ji, X. Wei, W. Wu, and C. Yang, “Asymmetric Photoreactions in Supramolecular Assemblies,” Accounts of Chemical Research 56 (2023): 1896–1907.
|
| [6] |
X. Tang, J. Qin, W. Xu, J.-F. Xu, and X. Zhang, “A Supramolecular Catalyst for Selective Photo-Oxidation With Catalytic Amount Enabled by Activating Substrates Into Radicals,” CCS Chemistry 7 (2025): 2044–2053.
|
| [7] |
J. Chen, Y.-L. Lu, Y. Huang, et al., “Asymmetric Cascade Photocycloaddition-Acyloin Rearrangement Enabled by Cage-Confined Visible-Light Catalysis,” Journal of the American Chemical Society 147 (2025): 13008–13016.
|
| [8] |
R. Saha, B. Mondal, and P. S. Mukherjee, “Molecular Cavity for Catalysis and Formation of Metal Nanoparticles for Use in Catalysis,” Chemical Reviews 122 (2022): 12244–12307.
|
| [9] |
Y. Nishioka, T. Yamaguchi, M. Yoshizawa, and M. Fujita, “Unusual [2+4] and [2+2] Cycloadditions of Arenes in the Confined Cavity of Self-Assembled Cages,” Journal of the American Chemical Society 129 (2007): 7000–7001.
|
| [10] |
Q.-Q. Wang, “Anion Recognition-Directed Supramolecular Catalysis With Functional Macrocycles and Molecular Cages,” Accounts of Chemical Research 57 (2024): 3227–3240.
|
| [11] |
T.-R. Li, F. Huck, G. Piccini, and K. Tiefenbacher, “Mimicry of the Proton Wire Mechanism of Enzymes Inside a Supramolecular Capsule Enables β-Selective O-Glycosylations,” Nature Chemistry 14 (2022): 985–994.
|
| [12] |
D. Fiedler, H. V. Halbeek, R. G. Bergman, and K. N. Raymond, “Supramolecular Catalysis of Unimolecular Rearrangements: Substrate Scope and Mechanistic Insights,” Journal of the American Chemical Society 128 (2006): 10240–10252.
|
| [13] |
L. J. Jongkind, X. Caumes, A. P. T. Hartendorp, and J. N. H. Reek, “Ligand Template Strategies for Catalyst Encapsulation,” Accounts of Chemical Research 51 (2018): 2115–2128.
|
| [14] |
A. Stank, D. B. Kokh, J. C. Fuller, and R. C. Wade, “Protein Binding Pocket Dynamics,” Accounts of Chemical Research 49 (2016): 809–815.
|
| [15] |
D. Zhang, L. Wang, W. Wu, D. Cao, and H. Tang, “Macrocyclic Catalysis Mediated by Water: Opportunities and Challenges,” Chemical Communications 61 (2025): 599–611.
|
| [16] |
C. J. Brown, F. D. Toste, R. G. Bergman, and K. N. Raymond, “Supramolecular Catalysis in Metal–Ligand Cluster Hosts,” Chemical Reviews 115 (2015): 3012–3035.
|
| [17] |
J. Han, H. Gong, X. Ren, and X. Yan, “Supramolecular Nanozymes Based on Peptide Self-Assembly for Biomimetic Catalysis,” Nano Today 41 (2021): 101295.
|
| [18] |
H. Nie, Z. Wei, X.-L. Ni, and Y. Liu, “Assembly and Applications of Macrocyclic-Confinement-Derived Supramolecular Organic Luminescent Emissions From Cucurbiturils,” Chemical Reviews 122 (2022): 9032–9077.
|
| [19] |
N. P. Dharmarajan, D. Vidyasagar, J.-H. Yang, et al., “Bio-Inspired Supramolecular Self-Assembled Carbon Nitride Nanostructures for Photocatalytic Water Splitting,” Advanced Materials 36 (2024): 2306895.
|
| [20] |
A. Bhattacharyya, D. S. Sarkar, and A. Das, “Supramolecular Engineering and Self-Assembly Strategies in Photoredox Catalysis,” ACS Catalysis 11 (2021): 710–733.
|
| [21] |
F. N. Tehrani, K. I. Assaf, R. Hein, C. M. E. Jensen, T. C. Nugent, and W. M. Nau, “Supramolecular Catalysis of a Catalysis-Resistant Diels–Alder Reaction: Almost Theoretical Acceleration of Cyclopentadiene Dimerization Inside Cucurbit[7]uril,” ACS Catalysis 12 (2022): 2261–2269.
|
| [22] |
M. Morimoto, S. M. Bierschenk, K. T. Xia, R. G. Bergman, K. N. Raymond, and F. D. Toste, “Advances in Supramolecular Host-Mediated Reactivity,” Nature Catalysis 3 (2020): 969–984.
|
| [23] |
Y. Jiao, B. Tang, Y. Zhang, J.-F. Xu, Z. Wang, and X. Zhang, “Highly Efficient Supramolecular Catalysis by Endowing the Reaction Intermediate With Adaptive Reactivity,” Angewandte Chemie International Edition 57 (2018): 6077–6081.
|
| [24] |
J. Liu, X. Han, N. Han, et al., “One-Pot ‘Click’ Synthesis of Ring-in-Rings Complexes With Customizable π-Stacked Dyads,” Journal of the American Chemical Society 147 (2025): 15838–15846.
|
| [25] |
G. Wu, F. Li, B. Tang, and X. Zhang, “Molecular Engineering of Noncovalent Dimerization,” Journal of the American Chemical Society 144 (2022): 14962–14975.
|
| [26] |
H. Yin, R. Rosas, S. Viel, et al., “Internal Dynamics and Modular Peripheral Binding in Stimuli-Responsive 3 : 2 Host: Guest Complexes,” Angewandte Chemie International Edition 63 (2024): e202315985.
|
| [27] |
M. Colaço, J. Ewert, J.-S. von Glasenapp, U. Pischel, R. Herges, and N. Basílio, “Diazocines as Guests of Cucurbituril Macrocycles: Light-Responsive Binding and Supramolecular Catalysis of Thermal Isomerization,” Journal of the American Chemical Society 147 (2025): 734–745.
|
| [28] |
K. Kanagaraj, R. Wang, M.-K. Zhao, P. Ballester, J. Rebek, and Y. Yu, “Selective Binding and Isomerization of Oximes in a Self-Assembled Capsule,” Journal of the American Chemical Society 145 (2023): 5816–5823.
|
| [29] |
K. Vega-Hernández, M. G. Suero, and P. Ballester, “Investing in Entropy: The Strategy of Cucurbit[n]urils to Accelerate the Intramolecular Diels–Alder Cycloaddition Reaction of Tertiary Furfuryl Amines,” Chemical Science 15 (2024): 8841–8849.
|
| [30] |
J. Wu, G. Wu, D. Li, and Y. Yang, “Macrocycle-Based Crystalline Supramolecular Assemblies Built With Intermolecular Charge-Transfer Interactions,” Angewandte Chemie International Edition 62 (2023): e202218142.
|
| [31] |
D. Sun, Y. Wu, X. Han, and S. Liu, “The Host–Guest Inclusion Driven by Host-Stabilized Charge Transfer for Construction of Sequentially Red-Shifted Mechanochromic System,” Nature Communications 14 (2023): 4190.
|
| [32] |
X. Ma and H. Tian, “Stimuli-Responsive Supramolecular Polymers in Aqueous Solution,” Accounts of Chemical Research 47 (2014): 1971–1981.
|
| [33] |
Y. H. Ko, E. Kim, I. Hwang, and K. Kim, “Supramolecular Assemblies Built With Host-Stabilized Charge-Transfer Interactions,” Chemical Communications (2007): 1305–1315.
|
| [34] |
X. Yang, R. Wang, A. Kermagoret, and D. Bardelang, “Oligomeric Cucurbituril Complexes: From Peculiar Assemblies to Emerging Applications,” Angewandte Chemie International Edition 59 (2020): 21280–21292.
|
| [35] |
J. Zhang, R. J. Coulston, S. T. Jones, J. Geng, O. A. Scherman, and C. Abell, “One-Step Fabrication of Supramolecular Microcapsules From Microfluidic Droplets,” Science 335 (2012): 690–694.
|
| [36] |
Q. Li, P. Zhang, P. Wang, et al., “A Combination of Covalent and Noncovalent Restricted-Intramolecular-Rotation Strategy for Supramolecular AIE-Type Photosensitizer Toward Photodynamic Therapy,” Aggregate 6 (2025): e676.
|
| [37] |
H. Nie, Y. Rao, J. Song, and X.-L. Ni, “Through-Space Conjugated Supramolecular Polymer Radicals From Spatial Organization of Cucurbit[8]uril: An Efficient Approach for Electron Transfer and Smart Photochromism Materials,” Chemistry of Materials 34 (2022): 8925–8934.
|
| [38] |
L. Striepe and T. Baumgartner, “Viologens and Their Application as Functional Materials,” Chemistry – A European Journal 23 (2017): 16924–16940.
|
| [39] |
R. Jeyaseelan, W. Liu, J. Zumbusch, and L. Næsborg, “Methyl Viologen as a Catalytic Acceptor for Electron Donor–Acceptor Photoinduced Cyclization Reactions,” Green Chemistry 27 (2025): 1969–1973.
|
| [40] |
X. Li, J. Yang, and Y.-W. Yang, “Recent Advances of Stimuli-Responsive Viologen-Based Nanocomposites,” Materials Chemistry Frontiers 7 (2023): 1463–1481.
|
| [41] |
B. Tang, W. Xu, J.-F. Xu, and X. Zhang, “Transforming a Fluorochrome to an Efficient Photocatalyst for Oxidative Hydroxylation: A Supramolecular Dimerization Strategy Based on Host-Enhanced Charge Transfer,” Angewandte Chemie International Edition 60 (2021): 9384–9388.
|
| [42] |
Y. Luo, H. Nie, C. Zou, Y. Fan, and X.-L. Ni, “Cucurbit[8]uril-Stabilized Charge Transfer: An Efficient Supramolecular Approach Toward a Heterogeneous Organic Photocatalyst for Aerobic Oxidation Reactions,” Chemistry – A European Journal 31 (2025): e202404273.
|
| [43] |
J. Chao, Y. Lei, Y. Yusran, H. Wang, D.-W. Zhang, and Z.-T. Li, “Supramolecular Organic Framework for Recyclable Heterogeneous Photocatalysis of the Reductive Dechlorination of α-Chloroacetophenones and Acetylation of Amines With Thioacetate,” Journal of Catalysis 428 (2023): 115146.
|
| [44] |
Y. Wang, C.-Q. Ma, X.-L. Li, et al., “A Novel Strategy of Constructing an Artificial Light-Harvesting System Based on a Supramolecular Organic Framework for Photocatalysis,” Journal of Materials Chemistry A 11 (2023): 2627–2633.
|
| [45] |
X. Yao, N. Han, H. Liu, and L. Xing, “Construction of Donor-Acceptor Supramolecular Organic Framework With Enhanced Superoxide Anion Radical Generation for Photocatalytic Synthesis of Benzimidazole,” Chinese Chemical Letters 36 (2025): 111426.
|
| [46] |
H. Nie, D. Hu, Z. Zeng, Y. Fan, Y. Zhai, and X.-L. Ni, “Cucurbit[8]uril-Regulated Face-to-Face Dimerization Assembly Enhanced Photosensitization and Photocatalysis,” Science China Chemistry 67 (2024): 1605–1612.
|
| [47] |
J. Lagona, P. Mukhopadhyay, S. Chakrabarti, and L. Isaacs, “The Cucurbit[n]uril Family,” Angewandte Chemie International Edition 44 (2005): 4844–4870.
|
| [48] |
J. Murray, K. Kim, T. Ogoshi, W. Yao, and B. C. Gibb, “The Aqueous Supramolecular Chemistry of Cucurbit[n]urils, Pillar[n]arenes and Deep-Cavity Cavitands,” Chemical Society Reviews 46 (2017): 2479–2496.
|
| [49] |
Z. Zhou, K. Yang, L. He, et al., “Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids With Symmetry Breaking Charge Transfer Contributing to NIR Emission Beyond 900 nm,” Journal of the American Chemical Society 146 (2024): 6763–6772.
|
| [50] |
T. Huang, K. Yang, W. Hu, et al., “Manipulation of Intramolecular Charge Transfer in NIR-II Emissive Organic Diradicaloids via a Symmetry-Breaking Design,” Chemistry 11 (2025): 102659.
|
| [51] |
Y. Fan, Y. Luo, X. Luo, and X.-L. Ni, “Single-Layer 2D Supramolecular-Organic-Framework-Supported Polyoxometalates: Efficient Selective Oxidation of Toluene in Seawater Under Sunlight,” Green Chemistry 26 (2024): 12076–12083.
|
| [52] |
B. R. Shah and U. D. Patel, “Mechanistic Aspects of Photocatalytic Degradation of Lindane by TiO2 in the Presence of Oxalic Acid and EDTA as Hole-Scavengers,” Journal of Environmental Chemical Engineering 9 (2021): 105458.
|
| [53] |
B. K. Kundu, G. Han, and Y. Sun, “Derivatized Benzothiazoles as Two-Photon-Absorbing Organic Photosensitizers Active Under Near Infrared Light Irradiation,” Journal of the American Chemical Society 145 (2023): 3535–3542.
|
| [54] |
P. K. Maitra, S. Bhattacharyya, N. Hickey, and P. S. Mukherjee, “Self-Assembly of a Water-Soluble Pd16 Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium,” Journal of the American Chemical Society 146 (2024): 15301–15308.
|
| [55] |
M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 09, Revision C.01 (Gaussian Inc., 2016).
|
RIGHTS & PERMISSIONS
2025 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.
PDF
