Tuning the electronic properties of hexanuclear cobalt sulfide superatoms <i>via</i> ligand substitution

Liu, Gaoxiang; Pinkard, Andrew; Ciborowski, Sandra M.; Chauhan, Vikas; Zhu, Zhaoguo; Aydt, Alexander P.; Khanna, Shiv N.; Roy, Xavier; Bowen, Kit H.

doi:10.1039/c8sc03862g

Cited by 29 publications

(34 citation statements)

References 53 publications

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“…Recently, photoelectron spectroscopy, photoabsorption spectroscopy, collision‐induced dissociation mass spectrometry, and ion‐mobility mass spectrometry have been applied to gain the intrinsic structure information in the absence of the external perturbation such as solvent and counter ion. [ 65,230,232,259–267 ]…”

Section: Discussionmentioning

confidence: 99%

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Omoda

Takano

Tsukuda

2020

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Atomically precise gold/silver clusters protected by organic ligands L, [(Au/Ag)xLy]z, have gained increasing interest as building units of functional materials because of their novel photophysical and physicochemical properties. The properties of [(Au/Ag)xLy]z are intimately associated with the quantized electronic structures of the metallic cores, which can be viewed as superatoms from the analogy of naked Au/Ag clusters. Thus, establishment of the correlation between the geometric and electronic structures of the superatomic cores is crucial for rational design and improvement of the properties of [(Au/Ag)xLy]z. This review article aims to provide a qualitative understanding on how the electronic structures of [(Au/Ag)xLy]z are affected by geometric structures of the superatomic cores with a focus on three factors: size, shape, and composition, on the basis of single‐crystal X‐ray diffraction data. The knowledge accumulated here will constitute a basis for the development of ligand‐protected Au/Ag clusters as new artificial elements on a nanometer scale.

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Section: Discussionmentioning

confidence: 99%

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Omoda

Takano

Tsukuda

2020

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“…These materials exhibit larger dielectric constants than organic semiconductors with profound consequences for their excitedstate properties, such as the ability to exploit quantum confinement effects. A variety of such molecular clusters, often referred to as superatoms, has already been used for the formation of solid-state materials [14][15][16][17][18] . A special interest is thereby focused on the influence of the structure of the assembled materials onto their properties, possibly enabling the creation of materials with desired properties by design 19,20 .…”

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confidence: 99%

Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

et al. 2020

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The collective properties of self-assembled nanoparticles with long-range order bear immense potential for customized electronic materials by design. However, to mitigate the shortcoming of the finite-size distribution of nanoparticles and thus, the inherent energetic disorder within assemblies, atomically precise nanoclusters are the most promising building blocks. We report an easy and broadly applicable method for the controlled self-assembly of atomically precise Au32(nBu3P)12Cl8 nanoclusters into micro-crystals. This enables the determination of emergent optoelectronic properties which resulted from long-range order in such assemblies. Compared to the same nanoclusters in glassy, polycrystalline ensembles, we find a 100-fold increase in the electric conductivity and charge carrier mobility as well as additional optical transitions. We show that these effects are due to a vanishing energetic disorder and a drastically reduced activation energy to charge transport in the highly ordered assemblies. This first correlation of structure and electronic properties by comparing glassy and crystalline self-assembled superstructures of atomically precise gold nanoclusters paves the way towards functional materials with novel collective optoelectronic properties.

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“…Recently, we have shown that the position of HOMO or LUMO in a variety of metal clusters can be tuned by using charge transfer ligands with electron-donating or accepting properties such as phosphine (PEt 3 , PMe 3 ), CO, CN as they bond and form surface dipoles. [41][42][43][44][45][46][47][48][49][50] We have also found that fused metal-chalcogenide clusters with unbalanced ligands may create intense internal electric fields that are ideal for separating electron-hole pairs in photon harvesting. 51 In this work, we have induced a diode-like shift in the conduction and valence level group of states on both sides of the bridged superatomic molecule by attaching N-ethyl-2-pyrrolidone (EP = C 6 H 11 NO) ligands on one of the PAl 12 clusters.…”

Section: Introductionmentioning

confidence: 95%

A ligand-induced homojunction between aluminum-based superatomic clusters

et al. 2020

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Tuning the electronic properties of hexanuclear cobalt sulfide superatoms via ligand substitution

Abstract: The electronic properties of the Co6S8L8 superatom can be tuned by changing its ligand composition while maintaining its electron count and closed shell.

Cited by 29 publications

References 53 publications

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

A ligand-induced homojunction between aluminum-based superatomic clusters

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