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.

Strongly Correlated Ladders in K-Doped p-Terphenyl Crystals.

Potassium-doped terphenyl has recently attracted attention as a potential host for high-transition-temperature superconductivity. Here, we elucidate the many-body electronic structure of recently synthesized potassium-doped terphenyl crystals. We show that this system may be understood as a set of weakly coupled one-dimensional ladders. Depending on the strength of the interladder coupling, the system may exhibit insulating spin-gapped valence-bond solid or antiferromagnetic phases, both of which upon hole doping may give rise to superconductivity. This terphenyl-based ladder material serves as a new platform for investigating the fate of ladder phases in the presence of three-dimensional coupling as well as for novel superconductivity.

Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular Chain: Antiferromagnetism in K-Doped p-Terphenyl.

Recent interest in potassium-doped p-terphenyl has been fueled by reports of superconductivity at Tc values surprisingly high for organic compounds. Despite these interesting properties, studies of the structure-function relationships within these materials have been scarce. Here, we isolate a phase-pure crystal of potassium-doped p-terphenyl: [K(222)]2[p-terphenyl3]. Emerging antiferromagnetism in the anisotropic structure is studied in depth by magnetometry and electron spin resonance. Combining these experimental results with density functional theory calculations, we describe the antiferromagnetic coupling in this system that occurs in all 3 crystallographic directions. The strongest coupling was found along the ends of the terphenyls, where the additional electron on neighboring p-terphenyls antiferromagnetically couple. This delocalized bonding interaction is reminiscent of the doubly degenerate resonance structure depiction of polyacetylene. These findings hint toward magnetic fluctuation-induced superconductivity in potassium-doped p-terphenyl, which has a close analogy with high Tc cuprate superconductors. The new approach described here is very versatile as shown by the preparation of two additional salts through systematic changing of the building blocks.

Air-stable, long-length, solution-based graphene nanoribbons.

Within the context of nanoelectronics, general strategies for the development of electronically tunable and air stable graphene nanoribbons are crucial. Previous studies towards the goal of processable nanoribbons have been complicated by ambient condition instability, insolubility arising from aggregation, or poor cyclization yield due to electron deficiency. Herein, we present a general strategy for the elongation of smaller graphene nanoribbon fragments into air-stable, easily processed, and electronically tunable nanoribbons. This strategy is facilitated by the incorporation of electron-rich donor units between electron-poor acceptor perylene diimide oligomeric units. The ribbons are processed in solution via a visible-light flow photocyclization using LEDs. The resulting long nanoribbons can be solution-cast and imaged, which are necessary characteristics for device fabrication. The ribbons become conductive after thermolysis of the pendent side-chains. The electron-accepting character of these nanoribbons in solution is reversible, and the conductivity of the thermolyzed species as a solid remains stable. This work highlights our general strategy for the mild and reliable fabrication of tunable and ambient-stable graphene nanoribbons, and charts a straightforward route for facile device incorporation.