Electron and Spin Delocalization in [Co6 Se8 (PEt3 )6 ]0/+1 Superatoms.

Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid-state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6 Se8 (PEt3 )6 . We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6 Se8 ] core while ligands function as an insulated shell. 59 Co SSNMR measurements on the core and 31 P, 13 C on the ligands show that the neutral Co6 Se8 (PEt3 )6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross-validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6 Se8 (PEt3 )6 ]+1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single-electron devices.

Singlet fission and triplet pair recombination in bipentacenes with a twist.

We investigate triplet pair dynamics in pentacene dimers that have varying degrees of coplanarity (pentacene-pentacene twist angle). The fine-tuning of the twist angle was achieved by alternating connectivity at the 1-position or 2-positions of pentacene. This mix-and-match connectivity leads to tunable twist angles between the two covalently linked pentacenes. These twisted dimers allow us to investigate the subtle effects that the dihedral angle between the covalently linked pentacenes imparts on singlet fission and triplet pair recombination dynamics. We observe that as the dihedral angle between the two bonded pentacenes is increased, the rates of singlet fission decrease, while the accompanying decrease in triplet recombination rates is stark. Temperature-dependent transient optical studies combined with theoretical calculations show that the triplet pair recombination proceeds primarily through a direct multiexciton internal conversion process. Calculations further show that the significant decrease in recombination rates can be directly attributed to a corresponding decrease in the magnitude of the nonadiabatic coupling between the singlet multiexcitonic state and the ground state. These results highlight the importance of the twist angle in designing systems that exhibit rapid singlet fission, while maintaining long triplet pair lifetimes in pentacene dimers.

Templated Polymerization of Nucleobase Complexes via Molecular Recognition.

Macromolecules have a strong tendency to interact with each other in solution to form a supramolecular structure through various secondary binding forces. In this study, nucleobase-containing templates poly(9-(4-vinylbenzyl)adenine) (PS AH) and poly(1-(4-vinylbenzyl)cytosine) (PS CH) are prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. Vinylbenzyl thymine (MS T) is polymerized in the presence of these two nucleobase-containing templates. MS T shows higher affinities toward the template PS AH compared with the template PS CH. In accordance with the Watson-Crick pairing principle, thymine forms hydrogen bonding (H-bonding) with adenine, but not between thymine and cytosine. A complex is formed when PS AH is used as template which indicates that there is a template polymerization of nucleobase complexes via molecular recognition.

Hierarchical Coherent Phonons in a Superatomic Semiconductor.

The coupling of phonons to electrons and other phonons plays a defining role in material properties, such as charge and energy transport, light emission, and superconductivity. In atomic solids, phonons are delocalized over the 3D lattice, in contrast to molecular solids where localized vibrations dominate. Here, a hierarchical semiconductor that expands the phonon space by combining localized 0D modes with delocalized 2D and 3D modes is described. This material consists of superatomic building blocks (Re6 Se8 ) covalently linked into 2D sheets that are stacked into a layered van der Waals lattice. Using transient reflectance spectroscopy, three types of coherent phonons are identified: localized 0D breathing modes of isolated superatom, 2D synchronized twisting of superatoms in layers, and 3D acoustic interlayer deformation. These phonons are coupled to the electronic degrees of freedom to varying extents. The presence of local phonon modes in an extended crystal opens the door to controlling material properties from hierarchical phonon engineering.

Spindle-like and telophase-like self-assemblies mediated by complementary nucleobase molecular recognition.

Inspired by nature, supramolecular nanoparticles based on complementary nucleobase interactions have aroused wide interest. In our study, two kinds of fluorophores were conjugated at the end of nucleobase containing homopolymers, which can be used to confirm the binding state and calculate the binding constants among different nucleobase pairs. Furthermore, we describe a facile synthesis of nucleobase-functionalized amphiphilic polymers with rigid and flexible backbones using RAFT polymerization. Spindle-like or telophase-like supramolecular self-assemblies were formed by different components of such synthetic amphiphilic polymers.

Polymer Synthesis with More Than One Form of Living Polymerization Method.

Controlled radical polymerization (CRP) or controlled/living radical polymerization has revolutionized the polymer industry as a tool for the preparation of a wide variety of polymers. This process enables the preparation of polymers with good control of molecular weight, narrow polydispersity, and a range of architectures including block and graft copolymers, star polymers, and other functional polymers. The mechanistic transformation reaction provides a great opportunity to tune chemical and physical properties of copolymers. It can be applied to combine different homopolymers using post-modification techniques or by the use of a dual initiator, allowing the combination of mechanistically distinct polymerization reactions. This review will cover CRP transformations including the synthesis of block copolymers with both linear structures (AB, ABA, (AB) n , multiblocks, etc.) and branched macromolecular architectures (graft, miktoarm star, and dendritic-like), which are obtained by a combination of more than one form of living polymerization reaction.

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.

Two-Dimensional Hierarchical Semiconductor with Addressable Surfaces.

Surfaces play a key role in determining material properties, and their importance is further magnified in the two-dimensional (2D) limit. Though monolayers are entirely composed of surfaces, there is no chemical approach to covalently address them without breaking intralayer bond. Here, we describe a 2D semiconductor that offers two unique features among 2D materials: structural hierarchy within the monolayer and surface reactive sites that enable functionalization. The 2D semiconductor is composed of a single layer of strongly interconnected Re6Se8 clusters arranged in an oblique lattice capped by substitutionally labile Cl atoms. We show that a simple ligand substitution strategy borrowed from traditional coordination chemistry can be used to modify the surface of the 2D material while preserving its internal structure. The potential generality of this approach establishes a promising route toward multifunctional 2D materials with tunable physical and chemical properties and may also facilitate better electrical top contact to 2D semiconductors.

Two-Dimensional Fullerene Assembly from an Exfoliated van der Waals Template.

Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C60 as a polymerizable monomer. The C60 building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C60 monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C60 . The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid.

Superatomic Two-Dimensional Semiconductor.

Structural complexity is of fundamental interest in materials science because it often results in unique physical properties and functions. Founded on this idea, the field of solid state chemistry has a long history and continues to be highly active, with new compounds discovered daily. By contrast, the area of two-dimensional (2D) materials is young, but its expansion, although rapid, is limited by a severe lack of structural diversity and complexity. Here, we report a novel 2D semiconductor with a hierarchical structure composed of covalently linked Re6Se8 clusters. The material, a 2D structural analogue of the Chevrel phase, is prepared via mechanical exfoliation of the van der Waals solid Re6Se8Cl2. Using scanning tunneling spectroscopy, photoluminescence and ultraviolet photoelectron spectroscopy, and first-principles calculations, we determine the electronic bandgap (1.58 eV), optical bandgap (indirect, 1.48 eV), and exciton binding energy (100 meV) of the material. The latter is consistent with the partially 2D nature of the exciton. Re6Se8Cl2 is the first member of a new family of 2D semiconductors whose structure is built from superatomic building blocks instead of simply atoms; such structures will expand the conceptual design space for 2D materials research.

Tuning Singlet Fission in π-Bridge-π Chromophores.

We have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet-triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.

Room-temperature current blockade in atomically defined single-cluster junctions.

Fabricating nanoscopic devices capable of manipulating and processing single units of charge is an essential step towards creating functional devices where quantum effects dominate transport characteristics. The archetypal single-electron transistor comprises a small conducting or semiconducting island separated from two metallic reservoirs by insulating barriers. By enabling the transfer of a well-defined number of charge carriers between the island and the reservoirs, such a device may enable discrete single-electron operations. Here, we describe a single-molecule junction comprising a redox-active, atomically precise cobalt chalcogenide cluster wired between two nanoscopic electrodes. We observe current blockade at room temperature in thousands of single-cluster junctions. Below a threshold voltage, charge transfer across the junction is suppressed. The device is turned on when the temporary occupation of the core states by a transiting carrier is energetically enabled, resulting in a sequential tunnelling process and an increase in current by a factor of ∼600. We perform in situ and ex situ cyclic voltammetry as well as density functional theory calculations to unveil a two-step process mediated by an orbital localized on the core of the cluster in which charge carriers reside before tunnelling to the collector reservoir. As the bias window of the junction is opened wide enough to include one of the cluster frontier orbitals, the current blockade is lifted and charge carriers can tunnel sequentially across the junction.

High Oxidation State Iridium Mono-µ-oxo Dimers Related to Water Oxidation Catalysis.

The highly active iridium "blue solution" chemical and electrochemical water oxidation catalyst obtained from Cp*IrL(OH) precursors (L = 2-pyridyl-2-propanoate) has been difficult to characterize as no crystal structure can be obtained because of the multiplicity of geometrical isomers present. Other data suggest complete loss of the Cp* ligand and the formation of a LIr-O-IrL unit. We have now developed a route to a series of well-defined Ir(IV,IV) mono-µ-oxo dimers, containing the closely related L2Ir-O-IrL2 unit. Unlike the catalyst, these model compounds are separable by silica gel chromatography and readily form single crystals. We report three stereoisomers with the formula ClL2Ir-O-IrL2Cl, which are fully characterized, including by X-ray crystallography, and are compared to the "blue solution". To the best of our knowledge, these species represent the first examples of structurally characterized dinuclear µ-oxo Ir(IV,IV) compounds without metal-carbon bonds.

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.

van der Waals Solids from Self-Assembled Nanoscale Building Blocks.

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.

Solvent-dependent conductance decay constants in single cluster junctions.

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.

Ligand Control of Manganese Telluride Molecular Cluster Core Nuclearity.

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 P(i)Pr3, PCy3, or (i)Pr2NHC ((i)Pr2NHC = 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((i)Pr2NHC)4 units to form the dicubane Mn8Te8((i)Pr2NHC)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.

Quantitative Intramolecular Singlet Fission in Bipentacenes.

Singlet fission (SF) has the potential to significantly enhance the photocurrent in single-junction solar cells and thus raise the power conversion efficiency from the Shockley-Queisser limit of 33% to 44%. Until now, quantitative SF yield at room temperature has been observed only in crystalline solids or aggregates of oligoacenes. Here, we employ transient absorption spectroscopy, ultrafast photoluminescence spectroscopy, and triplet photosensitization to demonstrate intramolecular singlet fission (iSF) with triplet yields approaching 200% per absorbed photon in a series of bipentacenes. Crucially, in dilute solution of these systems, SF does not depend on intermolecular interactions. Instead, SF is an intrinsic property of the molecules, with both the fission rate and resulting triplet lifetime determined by the degree of electronic coupling between covalently linked pentacene molecules. We found that the triplet pair lifetime can be as short as 0.5 ns but can be extended up to 270 ns.

Enantioselective copper-catalyzed reductive coupling of alkenylazaarenes with ketones.

Catalytic enantioselective methods for the preparation of chiral azaarene-containing compounds are of high value. By combining the utility of copper hydride catalysis with the ability of C═N-containing azaarenes to activate adjacent alkenes toward nucleophilic additions, the enantioselective reductive coupling of alkenylazaarenes with ketones has been developed. The process is tolerant of a wide variety of azaarenes and ketones, and provides aromatic heterocycles bearing tertiary-alcohol-containing side chains with high levels of diastereo- and enantioselection.

The immunization status of home-schooled children in America.

The immunization of children against a vast number of life-threatening infectious agents has been hailed as one of the greatest public health interventions of the twentieth century. In America, the morbidity and mortality associated with many common childhood infectious diseases has all but vanished. State-based school entry vaccination laws play a significant role in achieving high immunization rates among children and adolescents. Alarmingly, there is no consistent regulation in place to monitor the immunization status of the ever-growing home-schooled population. It is widely unknown whether the nearly 2 million home-schooled children are adequately immunized. As the home schooling movement continues to gain ground in the United States, pediatric nurse practitioners in the primary care setting will play an important role in protecting the health of these children, as well as the public's health.