Nature controls the assembly of complex architectures through self-limiting processes; however, few artificial strategies to mimic these processes have been reported to date. Here we demonstrate a system comprising two types of nanocrystal (NC), where the self-limiting assembly of one NC component controls the aggregation of the other. Our strategy uses semiconducting InP/ZnS core–shell NCs (3 nm) as effective assembly modulators and functional nanoparticle surfactants in cucurbit[n]uril-triggered aggregation of AuNCs (5–60 nm), allowing the rapid formation (within seconds) of colloidally stable hybrid aggregates. The resultant assemblies efficiently harvest light within the semiconductor substructures, inducing out-of-equilibrium electron transfer processes, which can now be simultaneously monitored through the incorporated surface-enhanced Raman spectroscopy–active plasmonic compartments. Spatial confinement of electron mediators (for example, methyl viologen (MV2+)) within the hybrids enables the direct observation of photogenerated radical species as well as molecular recognition in real time, providing experimental evidence for the formation of elusive σ–(MV+)2 dimeric species. This approach paves the way for widespread use of analogous hybrids for the long-term real-time tracking of interfacial charge transfer processes, such as the light-driven generation of radicals and catalysis with operando spectroscopies under irreversible conditions.
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Methods and materials characterization are provided in the Supplementary Information. The data that support the findings of this study are available from the corresponding author on reasonable request.
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We acknowledge financial support from EPSRC grant nos. EP/L027151/1 (NOtCH) and EP/R020965/1 (RaNT). J.H. is thankful for support from the Chinese Scholarship Council and Cambridge Commonwealth, European and International Trust. B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. R.C. acknowledges support from Trinity College, Cambridge. S.M.C. thanks Girton College, Cambridge, for a Henslow Research Fellowship. We thank S. J. Barrow, A. S. Groombridge and I. Szabó for helpful discussions. We acknowledge use of the research computing facility at King’s College London, Rosalind (https://rosalind.kcl.ac.uk).
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Hongyu Chen, Zhihong Nie and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Figs. 1–47, Table 1, discussion, materials and methods, and coordinates for the optimized structure.
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Sokołowski, K., Huang, J., Földes, T. et al. Nanoparticle surfactants for kinetically arrested photoactive assemblies to track light-induced electron transfer. Nat. Nanotechnol. 16, 1121–1129 (2021). https://doi.org/10.1038/s41565-021-00949-6