Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions

Shott, Jessica Lauren; Freeman, Matthew B.; Saleh, Nemah-Allah; Jones, Daniel S.; Paley, Daniel W.; Bejger, Christopher

doi:10.1021/acs.inorgchem.7b01259

Cited by 16 publications

(9 citation statements)

References 59 publications

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“…Comparing the crystallographic Co–P and Co–Co trans interatomic distances in [Co 6 Te 8 (PEt 3 ) 6 ][C 70 ] 2 with those measured in clusters [Co 6 Te 8 (PR 3 ) 6 ] n + of known oxidation states ( n = 0–2), we determine that Co 6 Te 8 (PEt 3 ) 6 bears a 1+ charge (Figure S4). On the basis of previous observations of dimerization in singly reduced C 70 compounds, , we conclude that the charges in [Co 6 Te 8 (PEt 3 ) 6 ][C 70 ] 2 are [Co 6 Te 8 (PEt 3 ) 6 + ][C 70 0 ][C 140 2– ] 1/2 . Crucially, the distortion of the CdI 2 trigonal superstructure, the interruption of the π-conjugation at the interfullerene C–C bond, and the localization and pairing of the transferred electrons into this bond all contribute to creating a fullerene network with weak extended π-hybridization.…”

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confidence: 60%

Spontaneous Electronic Band Formation and Switchable Behaviors in a Phase-Rich Superatomic Crystal

et al. 2018

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Structural phase transitions run in families of crystalline solids. Perovskites, for example, feature a remarkable number of structural transformations that produce a wealth of exotic behaviors, including ferroelectricity, magnetoresistance, metal–insulator transitions and superconductivity. In superatomic crystals and other such materials assembled from programmable building blocks, phase transitions offer pathways to new properties that are both tunable and switchable. Here we describe [Co6Te8(PEt3)6][C70]2, a novel superatomic crystal with two separate phase transitions that drastically transform the collective material properties. A coupled structural-electronic phase transition triggers the emergence of a new electronic band in the fullerene sublattice of the crystal, increasing its electrical conductivity by 2 orders of magnitude, while narrowing its optical gap and increasing its spin density. Independently, an order–disorder transition transforms [Co6Te8(PEt3)6][C70]2 from a phonon crystal to a phonon glass. These results introduce a family of materials in which functional phase transformations may be manipulated by varying the constituent building blocks.

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confidence: 60%

Spontaneous Electronic Band Formation and Switchable Behaviors in a Phase-Rich Superatomic Crystal

et al. 2018

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“…In each case, the inter-C 70 C–C distances within C 140 are ∼1.6 Å, which matches well with previously reported [C 140 ] 2– species (Table S4). − The trans Co–Co distances along the long axis in these compounds (∼10.2 Å) are shorter than that in neutral [Co 12 Se 16 (PEt 3 ) 10 ] (∼10.5 Å), but comparable to those in oxidized [Co 12 Se 16 (PEt 3 ) 10 ] species (∼10.2 Å in [Co 12 Se 16 (PEt 3 ) 10 ] + and ∼10.3 Å in [Co 12 Se 16 (PEt 3 ) 10 ] 2+ ; Table S4), indicating the oxidization of Co 12 Se 16 (PEt 3 ) 10 in the three crystals. Therefore, we conclude that the Co 12 Se 16 (PEt 3 ) 10 cluster bears a 1+ charge and the C 140 cluster bears a 2– charge.…”

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confidence: 90%

Shape Matching in Superatom Chemistry and Assembly

et al. 2020

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Creating structures with superatomic nanoclusters rather than atoms offers the possibility of new hierarchical solids with collective properties. The variability of chemical compositions, sizes, and shapes of these superatomic building blocks provides great opportunities to access unknown assemblies. Herein we explore this concept by using geometrically anisotropic superatomic nanoclusters as building blocks. We reveal a series of novel superatomic architectures that are built from rod-shaped Co12Se16(PEt3)10 and C140 nanoclusters. More importantly, these assemblies show nonclose packings that afford voids to accommodate solvent molecules as a result of the shape anisotropy of the constituent building blocks. These intercalated small molecules act as “crystal modulators” to modulate the solid-state structures and properties. As a result, we are able to tune the crystal packings and optical gaps of the solids and see the moment when electrical conduction is “turned on”. Our results demonstrate the vast potential of using anisotropic superatomic nanoclusters to create solid-state materials and provide a novel approach to configure their assemblies and properties.

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“…38 A similar dimerization process has been observed with C 70 in our hands and in recent work by Bejger. 49 However, this is the first example of a SAC containing an endohedral fullerene building block. The encapsulated Lu 3 N molecule displays a unique orientation that is collinear and coplanar with the intercage carbon bond, which is not observed in the other endohedral fullerene dimers.…”

Section: Sacs Self-assembled Via Charge Transfermentioning

confidence: 99%

Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials

2018

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The programmed assembly of nanoscale building blocks into multicomponent hierarchical structures is a powerful strategy for the bottom-up construction of functional materials. To develop this concept, our team has explored the use of molecular clusters as superatomic building blocks to fabricate new classes of materials. The library of molecular clusters is rich with exciting properties, including diverse functionalization, redox activity, and magnetic ordering, so the resulting cluster-assembled solids, which we term superatomic crystals (SACs), hold the promise of high tunability, atomic precision, and robust architectures among a diverse range of other material properties. Molecular clusters have only seldom been used as precursors for functional materials. Our team has been at the forefront of new developments in this exciting research area, and this Account focuses on our progress toward designing materials from cluster-based precursors. In particular, this Account discusses (1) the design and synthesis of molecular cluster superatomic building blocks, (2) their self-assembly into SACs, and (3) their resulting collective properties. The set of molecular clusters discussed herein is diverse, with different cluster cores and ligand arrangements to create an impressive array of solids. The cluster cores include octahedral ME and cubane ME (M = metal; E = chalcogen), which are typically passivated by a shell of supporting ligands, a feature upon which we have expanded upon by designing and synthesizing more exotic ligands that can be used to direct solid-state assembly. Building from this library, we have designed whole families of binary SACs where the building blocks are held together through electrostatic, covalent, or van der Waals interactions. Using single-crystal X-ray diffraction (SCXRD) to determine the atomic structure, a remarkable range of compositional variability is accessible. We can also use this technique, in tandem with vibrational spectroscopy, to ascertain features about the constituent superatomic building blocks, such as the charge of the cluster cores, by analysis of bond distances from the SCXRD data. The combination of atomic precision and intercluster interactions in these SACs produces novel collective properties, including tunable electrical transport, crystalline thermal conductivity, and ferromagnetism. In addition, we have developed a synthetic strategy to insert redox-active guests into the superstructure of SACs via single-crystal-to-single-crystal intercalation. This intercalation process allows us to tune the optical and electrical transport properties of the superatomic crystal host. These properties are explored using a host of techniques, including Raman spectroscopy, SQUID magnetometry, electrical transport measurements, electronic absorption spectroscopy, differential scanning calorimetry, and frequency-domain thermoreflectance. Superatomic crystals have proven to be both robust and tunable, representing a new method of materials design and architecture. This Account demon...

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Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions

Cited by 16 publications

References 59 publications

Spontaneous Electronic Band Formation and Switchable Behaviors in a Phase-Rich Superatomic Crystal

Spontaneous Electronic Band Formation and Switchable Behaviors in a Phase-Rich Superatomic Crystal

Shape Matching in Superatom Chemistry and Assembly

Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials

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