We report a series of single-molecule transport measurements carried out in an ionic environment with oligophenylenediamine wires. These molecules exhibit three discrete conducting states accessed by electrochemically modifying the contacts. Transport in these junctions is defined by the oligophenylene backbone, but the conductance is increased by factors of ∼20 and ∼400 when compared to traditional dative junctions. We propose that the higher-conducting states arise from in situ electrochemical conversion of the dative Au←N bond into a new type of Au–N contact. Density functional theory-based transport calculations establish that the new contacts dramatically increase the electronic coupling of the oligophenylene backbone to the Au electrodes, consistent with experimental transport data. The resulting contact resistance is the lowest reported to date; more generally, our work demonstrates a facile method for creating electronically transparent metal–organic interfaces.

Traditional atomic van der Waals materials such as graphene, hexagonal boron-nitride, and transition metal dichalcogenides have received widespread attention due to the wealth of unusual physical and chemical behaviors that arise when charges, spins, and vibrations are confined to a plane. Though not as widespread as their atomic counterparts, molecule-based two-dimensional (2D) layered solids offer significant benefits; their structural flexibility will enable the development of materials with tunable properties. Here we describe a layered van der Waals solid self-assembled from a structure-directing building block and C60 fullerene. The resulting crystalline solid contains a corrugated monolayer of neutral fullerenes and can be mechanically exfoliated. The absorption spectrum of the bulk solid shows an optical gap of 390 ± 40 meV that is consistent with thermal activation energy obtained from electrical transport measurement. We find that the dimensional confinement of fullerenes significantly modulates the optical and electronic properties compared to the bulk solid.

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.Keywords: nanoscale atoms; nanoscale building blocks; superatom molecules; Superatoms;

This study describes a new and simple approach to dope two-dimensional transition metal dichalcogenides (TMDCs) using the superatom Co6Se8(PEt3)6 as the electron dopant. Semiconducting TMDCs are wired into field-effect transistor devices and then immersed into a solution of these superatoms. The degree of doping is determined by the concentration of the superatoms in solution and by the length of time the films are immersed in the dopant solution. Using this chemical approach, we are able to turn mono- and few-layer MoS2 samples from moderately to heavily electron-doped states. The same approach applied on WSe2 films changes their characteristics from hole transporting to electron transporting. Moreover, we show that the superatom doping can be patterned on specific areas of TMDC films. To illustrate the power of this technique, we demonstrate the fabrication of a lateral p–n junction by selectively doping only a portion of the channel in a WSe2 device. Finally, encapsulation of the doped films with crystalline hydrocarbon layers stabilizes their properties in an ambient environment.

Single-molecule conductance measurements have focused primarily on organic molecular systems. Here, we carry out scanning tunneling microscope-based break-junction measurements on a series of metal chalcogenide Co6Se8 clusters capped with conducting ligands of varying lengths. We compare these measurements with those of individual free ligands and find that the conductance of these clusters and the free ligands have different decay constants with increasing ligand length. We also show, through measurements in two different solvents, 1-bromonaphthalene and 1,2,4-trichlorobenzene, that the conductance decay of the clusters depends on the solvent environment. We discuss several mechanisms to explain our observations.

We report the synthesis, structural diversity, and chemical behavior of a family of manganese telluride molecular clusters whose charge-neutral cores are passivated by two-electron donor ligands. We describe three different core structures: a cubane-type Mn4Te4, a prismane Mn6Te6, and a dicubane Mn8Te8. We use various trialkylphosphines and N-heterocyclic carbenes (NHCs) as surface ligands and demonstrate that the formation of the different cluster core structures is controlled by the choice of ligand: bulky ligands such as PiPr3, PCy3, or iPr2NHC (iPr2NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) form the cubane-type core, while the smaller PMe3 produces the prismane core. The intermediate-sized PEt3 produces both cubane and prismane species. These manganese telluride molecular clusters are labile, and the capping phosphines can be replaced by stronger ligands, while the internal core structure of the cluster remains intact. The interplay of structural diversity and ligand versatility and lability makes these clusters potentially useful building blocks for the assembly of larger aggregates and extended structures. We demonstrate the simplest prototype of these solid-forming reactions: the direct coupling of two Mn4Te4(iPr2NHC)4 units to form the dicubane Mn8Te8(iPr2NHC)6. We also postulate the prismatic Mn6Te6 as the common ancestor of both Chevrel-type M6E8 and octanuclear rhombododecahedral M8E6 molecular clusters (M = transition metal and E = chalcogen), and we discuss the core structure of our molecular clusters as recognizable building units for the zinc blende and the hypothetical wurtzite lattices of MnTe.

In order to realize significant benefits from the assembly of solid-state materials from molecular cluster superatomic building blocks, several criteria must be met. Reproducible syntheses must reliably produce macroscopic amounts of pure material; the cluster-assembled solids must show properties that are more than simply averages of those of the constituent subunits; and rational changes to the chemical structures of the subunits must result in predictable changes in the collective properties of the solid. In this report we show that we can meet these requirements. Using a combination of magnetometry and muon spin relaxation measurements, we demonstrate that crystallographically defined superatomic solids assembled from molecular nickel telluride clusters and fullerenes undergo a ferromagnetic phase transition at low temperatures. Moreover, we show that when we modify the constituent superatoms, the cooperative magnetic properties change in predictable ways.

Hierarchical solids created from the binary assembly of cobalt chalcogenide and iron oxide molecular clusters are reported. Six different molecular clusters based on the octahedral Co6E8 (E = Se or Te) and the expanded cubane Fe8O4 units are used as superatomic building blocks to construct these crystals. The formation of the solid is driven by the transfer of charge between complementary electron-donating and electron-accepting clusters in solution that crystallize as binary ionic compounds. The hierarchical structures are investigated by single-crystal X-ray diffraction, providing atomic and superatomic resolution. We report two different superstructures: a superatomic relative of the CsCl lattice type and an unusual packing arrangement based on the double-hexagonal close-packed lattice. Within these superstructures, we demonstrate various compositions and orientations of the clusters.