Controlling Ligand Coordination Spheres and Cluster Fusion in Superatoms.

We show that reaction pathways from a single superatom motif can be controlled through subtle electronic modification of the outer ligand spheres. Chevrel-type [Co6Se8L6] (L = PR3, CO) superatoms are used to form carbene-terminated clusters, the reactivity of which can be influenced through the electronic effects of the surrounding ligands. This carbene provides new routes for ligand substitution chemistry, which is used to selectively install cyanide or pyridine ligands which were previously inaccessible in these cobalt-based clusters. The surrounding ligands also impact the ability of this carbene to create larger fused clusters of the type [Co12Se16L10], providing underlying information for cluster fusion mechanisms. We use this information to develop methods of creating dimeric clusters with functionalized surface ligands with site specificity, putting new ligands in specific positions on this anisotropic core. Finally, adjusting the carbene intermediates can also be used to perturb the geometry of the [Co6Se8] core itself, as we demonstrate with a multicarbene adduct that displays a substantially anisotropic core. These additional levels of synthetic control could prove instrumental for using superatomic clusters for many applications including catalysis, electronic devices, and creating novel extended structures.

Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials.

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 M6E8 and cubane M4E4 (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 demonstrates how precisely controlling the structure and properties of nanoscale building blocks is key in developing the next generation of functional materials; several examples are discussed and detailed herein.

Superatom Fusion and the Nature of Quantum Confinement.

Quantum confinement endows colloidal semiconducting nanoparticles with many fascinating and useful properties, yet a critical limitation has been the lack of atomic precision in their size and shape. We demonstrate the emergence of quantum confined behavior for the first time in atomically defined Co6Se8(PEt3)6 superatoms by dimerizing [Co6Se8] units through direct fusion. To accomplish this dimerization, we install a reactive carbene on the [Co6Se8] core to create a latent fusion site. Then we transform the reactive carbene intermediate into a material with an expanded core, [Co12Se16], that exhibits electronic and optical properties distinct from the parent monomer. The chemical transformation presented herein allows for precise synthetic control over the ligands and size of these clusters. We show by cyclic voltammetry, infrared spectroscopy, single crystal X-ray diffraction, and density functional theory calculations that the resulting fused [Co12Se16] material exhibits strong electronic coupling and electron delocalization. We observe a bandgap reduction upon expanding the cluster core, suggesting that we have isolated a new intermediate in route to extended solids. These results are further corroborated with electronic structure calculations of a monomer, fused dimer, trimer, and tetramer species. These reactions will allow for the synthesis of extended highly delocalized wires, sheets, and cages.

Electron Cartography in Clusters.

Deconvoluting the atom-specific electron density within polynuclear systems remains a challenge. A multiple-wavelength anomalous diffraction study on four clusters that share the same [Co6 Se8 ] core was performed. Two cluster types were designed, one having a symmetric ligand sphere and the other having an asymmetric ligand sphere. It was found that in the neutral, asymmetric, CO-bound cluster, the Co-CO site is more highly oxidized than the other five Co atoms; when an electron is removed, the hole is distributed among the Se atoms. In the neutral, symmetric cluster, the Co atoms divide by electron population into two sets of three, each set being meridional; upon removal of an electron, the hole is distributed among all the Co atoms. This ligand-dependent tuning of the electron/hole distribution relates directly to the performance of clusters in biological and synthetic systems.

Weaving Nanoscale Cloth through Electrostatic Templating.

Here we disclose a simple route to nanoscopic 2D woven structures reminiscent of the methods used to produce macroscopic textiles. We find that the same principles used in macroscopic weaving can be applied on the nanoscale to create two-dimensional molecular cloth from polymeric strands, a molecular thread. The molecular thread is composed of Co6Se8(PEt3)4L2 superatoms that are bridged with L = benzene bis-1,4-isonitrile to form polymer strands. As the superatoms that make up the polymer chain are electrochemically oxidized, they are electrostatically templated by a nanoscale anion, the tetragonal Lindqvist polyoxometalate Mo6O192-. The tetragonal symmetry of the dianionic template creates a nanoscale version of the box weave. The crossing points in the weave feature π-stacking of the bridging linker. By examining the steps in the weaving process with single crystal X-ray diffraction, we find that the degree of polymerization at the crossing points is crucial in the cloth formation. 2D nanoscale cloth will provide access to a new generation of smart, multifunctional materials, coatings, and surfaces.

Building Diatomic and Triatomic Superatom Molecules.

In this study, we have developed a method to create Co6Se8 superatoms in which we program the metal-ligand bonds. We exclusively form the Co6Se8 core under simple reaction conditions with a facile separation of products that contain differential substitution of the core. The combination of Co2(CO)8 and PR3 with excess Se gives the differentially and directionally substituted superatoms, Co6Se8(CO)x(PR3)(6-x). The CO groups on the superatom can be exchanged quantitatively with phosphines and isonitriles. Substitution of the CO allows us to manipulate the type and length of chemical bridge between two redox-active superatomic centers in order to modulate intersuperatomic coupling. Linking two superatoms together allows us to form the simplest superatom molecule: a diatomic molecule. We extend the superatom molecule concept to link three superatoms together in a linear arrangement to form acyclic triatomic molecules. These superatom molecules have a rich electrochemical profile and chart a clear path to a whole family of superatom molecules with new and unusual collective properties.

Two-Dimensional Nanosheets from Redox-Active Superatoms.

We describe a new approach to synthesize two-dimensional (2D) nanosheets from the bottom-up. We functionalize redox-active superatoms with groups that can direct their assembly into multidimensional solids. We synthesized Co6Se8[PEt2(4-C6H4COOH)]6 and found that it forms a crystalline assembly. The solid-state structure is a three-dimensional (3D) network in which the carboxylic acids form intercluster hydrogen bonds. We modify the self-assembly by replacing the reversible hydrogen bonds that hold the superatoms together with zinc carboxylate bonds via the solvothermal reaction of Co6Se8[PEt2(4-C6H4COOH)]6 with Zn(NO3)2. We obtain two types of crystalline materials using this approach: one is a 3D solid and the other consists of stacked layers of 2D sheets. The dimensionality is controlled by subtle changes in reaction conditions. These 2D sheets can be chemically exfoliated, and the exfoliated, ultrathin 2D layers are soluble. After they are deposited on a substrate, they can be imaged. We cast them onto an electrode surface and show that they retain the redox activity of the superatom building blocks due to the porosity in the sheets.