Template‐Free Supracolloidal Self‐Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids

Nonappa, Nonappa; Lahtinen, Tanja; Haataja, Johannes S.; Tero, Tiia‐Riikka; Häkkinen, Hannu; Ikkala, Olli

doi:10.1002/ange.201609036

Cited by 22 publications

(6 citation statements)

References 37 publications

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“…Nonappa et al discovered 12 an interesting spontaneous selfassembly of Au 102 (pMBA) 44 clusters into 2D flakes and 3D spherical capsids in water-methanol mixtures. The superstructures were up to 500 nm in size and could be reversibly assembled and de-assembled by controlling the solvent conditions.…”

Section: Self-assembly and Cluster-based Materialsmentioning

confidence: 99%

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Prospects and challenges for computer simulations of monolayer-protected metal clusters

Malola

Häkkinen

2021

Nat Commun

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Precise knowledge of chemical composition and atomic structure of functional nanosized systems, such as metal clusters stabilized by an organic molecular layer, allows for detailed computational work to investigate structure-property relations. Here, we discuss selected recent examples of computational work that has advanced understanding of how these clusters work in catalysis, how they interact with biological systems, and how they can make self-assembled, macroscopic materials. A growing challenge is to develop effective new simulation methods that take into account the cluster-environment interactions. These new hybrid methods are likely to contain components from electronic structure theory combined with machine learning algorithms for accelerated evaluations of atom-atom interactions.Monolayer-protected metal clusters (MPCs) are hybrid metal nanoparticles consisting of a metal core and a protecting layer of organic ligand molecules. They have a precise mass and chemical composition, and in many cases their structure is known to atomic precision 1 . During the last decade, experimental and computational investigations of MPCs have burgeoned, yielding ample novel information about physical, chemical, catalytic, optical, biological and medical properties of these atomically defined nanomaterials 1 . The often precise knowledge of the MPCs' atomic structure creates an excellent starting point to use various atomistic simulation tools to understand their structure-property relations. However, MPCs can have complex interactions with their environments, which creates challenges to simulations due to needed length scales, time scales or the need to describe the complex chemical interactions properly on an equal footing.As Fig. 1 illustrates, there are currently several methods that can be used for computational investigations of MPCs' physical and chemical properties. Quantum-chemical (QC) methods are based on optimizing the total many-body wave function of the quantum system (a function of 3N components for N atoms). They can conveniently deal with small molecules with great chemical accuracy and have traditionally provided benchmark results for strengths of various chemical bonds. However, their application area is still limited to small systems on the order of 10 metal atoms. Density functional theory (DFT) is a major workhorse dealing with MPCs' electronic structure, optical properties and reactions. DFT uses the total electron density of the system (a function of 3 components) as the basic physical variable, reducing the complexity of the ground-state problem immensely as compared to QC methods. With modern massively

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Section: Self-assembly and Cluster-based Materialsmentioning

confidence: 99%

“…We thank all our co-authors in refs. [1][2][3][6][7][8][9][10][11][12][13][14]16,[19][20][21] for inspiring collaborations. This research has been supported by the Academy of Finland (grants 292352, 294217, 315549, 319208).…”

Section: Acknowledgementsmentioning

confidence: 99%

Prospects and challenges for computer simulations of monolayer-protected metal clusters

Malola

Häkkinen

2021

Nat Commun

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“…Interestingly, aqueous and monodispersed Au 102 ‐ p ‐mercaptobenzoic acid ( p MBA) 44 nanoclusters have been simultaneously assembled as building blocks into hollow spherical superstructures in a water and methanol mixture . A uniform and stable monolayer shell was formed based on the amphiphilic nature of the nanoclusters.…”

Section: Architectural Strategies For Assembled Hollow Superstructuresmentioning

confidence: 99%

Architectural Design of Self‐Assembled Hollow Superstructures

et al. 2018

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Colloidal nanoparticle assemblies are widely designed and fabricated via various building blocks to enhance their intrinsic properties and potential applications. Self-assembled hollow superstructures have been a focal point in nanotechnology for several decades and are likely to remain so for the foreseeable future. The novel properties of self-assembled hollow superstructures stem from their effective spatial utilization. As such, a comprehensive appreciation of the interactive forces at play among individual building blocks is a prerequisite for designing and managing the self-assembly process, toward the fabrication of optimal hollow nanoproducts. Herein, the emerging approaches to the fabrication of self-assembled hollow superstructures, including hard-templated, soft-templated, self-templated, and template-free methods, are classified and discussed. The corresponding reinforcement mechanisms, such as strong ligand interaction strategies and extra-capping strategies, are discussed in detail. Finally, possible future directions for the construction of multifunctional hollow superstructures with highly efficient catalytic reaction systems and an integration platform for bioapplications are discussed.

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“…Such novel materials can find applications in advanced optical materials due to their collective and enhanced optical properties that arise from the periodic organization. Recently, NC self-assembly was realized via dipole-induced van der Waals attraction, 31 hydrogen bonding, 32 C-H..p interactions, 33 metal chelation, 34 and aurophilic interactions. 35 Importantly, self-assembled gold NC superstructures have been shown to alter the luminescence, catalytic activity and bioavailability.…”

Section: Introductionmentioning

confidence: 99%

Light-Triggered Reversible Supracolloidal Self-Assembly of Precision Gold Nanoclusters

Rival

Nonappa

Shibu

2020

ACS Appl. Mater. Interfaces

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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 resulted in a visual change and formation of disc-like colloidal superstructures (d ~100 -1000 nm). The superstructures readily disassembled into individual nanoclusters upon irradiating with the 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 self-assembly is driven by the photoisomerization of surface ligands. 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 photo-switching in nanoclusters.NCs). Dried [Au25(C3-AMT)18] -NCs were stored at 4 ºC for further characterizations. ASSOCIATED CONTENT Supporting InformationThe Supporting Information is available free of charge on the ACS Publications website. Scheme S1, S2 and Figures S1-S17 as described in the text (PDF) Video S1 as described in the text (MOV)

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Template‐Free Supracolloidal Self‐Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids

Cited by 22 publications

References 37 publications

Prospects and challenges for computer simulations of monolayer-protected metal clusters

Prospects and challenges for computer simulations of monolayer-protected metal clusters

Architectural Design of Self‐Assembled Hollow Superstructures

Light-Triggered Reversible Supracolloidal Self-Assembly of Precision Gold Nanoclusters

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