Light-Triggered Reversible Supracolloidal Self-Assembly of Precision Gold Nanoclusters (original) (raw)
Research ArticleMarch 3, 2020
Light-Triggered Reversible Supracolloidal Self-Assembly of Precision Gold Nanoclusters
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- Jose V. Rival
Smart Materials Lab, Functional Materials Division, Council of Scientific and Industrial Research (CSIR)-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India - Nonappa
Nonappa
Department of Applied Physics, Aalto University School of Science, Puumiehenkuja 2, Espoo FI-02150, Finland - Edakkattuparambil Sidharth Shibu*
Edakkattuparambil Sidharth Shibu
Smart Materials Lab, Functional Materials Division, Council of Scientific and Industrial Research (CSIR)-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India
Academy of Scientific and Innovative Research (AcSIR)-CSIR, Ghaziabad 201002, Uttar Pradesh, India
*****Email: [email protected] or [email protected]
ACS Applied Materials & Interfaces
Cite this: ACS Appl. Mater. Interfaces 2020, 12, 12
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Copyright © 2020 American Chemical Society
Abstract
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Monolayer thiol-protected noble metal nanoclusters are attractive nanoscale building blocks for well-defined colloidal superstructures. However, achieving facile reversible self-assembly of nanoclusters using external stimuli is still in its infancy. Herein, we report the synthesis and photon-assisted reversible self-assembly of thiolated azobenzene-stapled Au25 nanoclusters. Photoactivation of functionalized nanoclusters in dichloromethane by irradiating ultraviolet light at 345 nm results in a visual change and formation of disc-like colloidal superstructures (d ∼ 100–1000 nm). The superstructures readily disassemble into individual nanoclusters upon irradiating with visible light at 435 nm. Systematic changes in both the electronic absorption bands and nuclear magnetic resonance spectra of chromophores in solution suggest that the photoisomerization of surface ligands drives the self-assembly. High-resolution transmission electron microscopy, electron tomographic reconstruction, dynamic light scattering, and small-angle X-ray powder diffraction show that the disc-like superstructures contain densely packed nanoclusters. Long-range self-assembly and disassembly under ultraviolet and visible light, respectively, demonstrate reversible photoswitching in nanoclusters.
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Supporting Information
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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c00328.
Scheme for the synthesis of molecules 1–3 (C3-AMT); 1H and 13C NMR, LC–MS, and FT-IR spectra of molecules; temporal absorption spectra of C3-AMT and [Au25(C3-AMT)18]–; XPS spectra of NCs; mechanism for the dipole-induced self-assembly; photographs of NC solution during the course of assembly and disassembly; large-area TEM micrographs of assembly and disassembly; Temporal absorption spectra of self-assembled superstructures and trans NCs under dark; TEM images of [Au25(PET)18]– before and after light illumination; TEM images of self-assembled dimer; elemental maps and EDS spectum of superstructure; temporal DLS spectra of assembly and disassembly; dark-field scattering image of superstructures; cross-sectional views of 3D-reconstructed disc-like superstructures (PDF)
Three-dimensional superstructures are composed of densely packed NCs (MOV)
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Cite this: ACS Appl. Mater. Interfaces 2020, 12, 12
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