Nanoscale Atoms in Solid-State Chemistry

Roy, Xavier; Lee, Chul‐Ho; Crowther, Andrew C.; Schenck, Christine L.; Besara, Tiglet; Lalancette, Roger A.; Siegrist, T.; Stephens, Peter W.; Brus, L. E.; Kim, Philip; Steigerwald, Michael L.; Nuckolls, Colin

doi:10.1126/science.1236259

Cited by 224 publications

(244 citation statements)

References 22 publications

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“…We also expect that the clusters with controllable size can be used as versatile precursors for synthetic implications such as nanopreparation 37 and superlattice assembly. 39,40 …”

Section: Discussionmentioning

confidence: 98%

Role of Anions Associated with the Formation and Properties of Silver Clusters

2015

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Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.

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“…We also expect that the clusters with controllable size can be used as versatile precursors for synthetic implications such as nanopreparation 37 and superlattice assembly. 39,40 …”

Section: Discussionmentioning

confidence: 98%

Role of Anions Associated with the Formation and Properties of Silver Clusters

2015

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“…Ordered molecular clusters1, nanoparticle superlattices2 and colloidal crystals3 have been extensively pursued in order to develop hierarchically structured nanomaterials with tuneable optical, magnetic, electronic and catalytic properties45. Binary and ternary crystals have received focused attention because they provide an approach to integrate different components to yield multifunctional metamaterials, where new properties arise from collective behaviour67.…”

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confidence: 99%

Self-assembly and modular functionalization of three-dimensional crystals from oppositely charged proteins

2014

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Multicomponent crystals and nanoparticle superlattices are a powerful approach to integrate different materials into ordered nanostructures. Well-developed, especially DNA-based, methods for their preparation exist, yet most techniques concentrate on molecular and synthetic nanoparticle systems in non-biocompatible environment. Here we describe the self-assembly and characterization of binary solids that consist of crystalline arrays of native biomacromolecules. We electrostatically assembled cowpea chlorotic mottle virus particles and avidin proteins into heterogeneous crystals, where the virus particles adopt a non-close-packed body-centred cubic arrangement held together by avidin. Importantly, the whole preparation process takes place at room temperature in a mild aqueous medium allowing the processing of delicate biological building blocks into ordered structures with lattice constants in the nanometre range. Furthermore, the use of avidin–biotin interaction allows highly selective pre- or post-functionalization of the protein crystals in a modular way with different types of functional units, such as fluorescent dyes, enzymes and plasmonic nanoparticles.

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“…24 have now appeared in the literature and are referred to as "nanoscale atom mimicry" at the nanoscale. In each case, our early concept has been fulfilled and validated by these authors, who have referred to these nanoscale building blocks as "atom equivalents" (i.e., Mirkin and coworkers [146]) or "nanoscale atoms" (i.e., Roy, Brus and coworkers [168] ), a solid-state material is formed that they described as a "super atomic relative" of the cadmium iodide (CdI 2 ) structure type. Furthermore, they stated that the constituent clusters (i.e., [H-5] and [H-2]) interacted electronically to produce a magnetically ordered phase at low temperature, akin to atoms in a solid-state compound.…”

Section: Combining Soft and Hard Nano-element Categoriesmentioning

confidence: 99%

Hierarchical Macromolecular Structures: 60 Years after the Staudinger Nobel Prize I

2013

Advances in Polymer Science

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Nanoscale Atoms in Solid-State Chemistry

Cited by 224 publications

References 22 publications

Role of Anions Associated with the Formation and Properties of Silver Clusters

Role of Anions Associated with the Formation and Properties of Silver Clusters

Self-assembly and modular functionalization of three-dimensional crystals from oppositely charged proteins

Hierarchical Macromolecular Structures: 60 Years after the Staudinger Nobel Prize I

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