Synthesis of graded CdS1-xSex nanoplatelet alloys and heterostructures from pairs of chalcogenoureas with tailored conversion reactivity.

A mixture of N,N,N'-trisubstituted thiourea and cyclic N,N,N',N'-tetrasubstituted selenourea precursors were used to synthesize three monolayer thick CdS1-xSex nanoplatelets in a single synthetic step. The microstructure of the nanoplatelets could be tuned from homogeneous alloys, to graded alloys to core/crown heterostructures depending on the relative conversion reactivity of the sulfur and selenium precursors. UV-visible absorption and photoluminescence spectroscopy and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) images demonstrate that the elemental distribution is governed by the relative precursor conversion kinetics. Slow conversion kinetics produced nanoplatelets with larger lateral dimensions, behavior that is characteristic of precursor conversion limited growth kinetics. Across a 10-fold range of reactivity, CdS nanoplatelets have 4× smaller lateral dimensions than CdSe nanoplatelets grown under identical conversion kinetics. The difference in size is consistent with a rate of CdSe growth that is 4× greater than the rate of CdS. The influence of the relative sulfide and selenide growth rates, the duration of the nucleation phase, and the solute composition on the nanoplatelet microstructure are discussed.

A few-layer covalent network of fullerenes.

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp3-hybridized and sp2-hybridized atoms, respectively1. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C60 that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices2. The synthesis entails growing single crystals of layered polymeric (Mg4C60)∞ by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C60, which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices3. More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties.

Superatom Regiochemistry Dictates the Assembly and Surface Reactivity of a Two-Dimensional Material.

The area of two-dimensional (2D) materials research would benefit greatly from the development of synthetically tunable van der Waals (vdW) materials. While the bottom-up synthesis of 2D frameworks from nanoscale building blocks holds great promise in this quest, there are many remaining hurdles, including the design of building blocks that reliably produce 2D lattices and the growth of macroscopic crystals that can be exfoliated to produce 2D materials. Here we report the regioselective synthesis of the cluster [trans-Co6Se8(CN)4(CO)2]3-/4-, a "superatomic" building block designed to polymerize and assemble into a 2D cyanometalate lattice whose surfaces are chemically addressable. The resulting vdW material, [Co(py)4]2[trans-Co6Se8(CN)4(CO)2], grows as bulk single crystals that can be mechanically exfoliated to produce flakes as thin as bilayers, with photolabile CO ligands on the exfoliated surface. As a proof of concept, we show that these surface CO ligands can be replaced by 4-isocyanoazobenzene under blue light irradiation. This work demonstrates that the bottom-up assembly of layered vdW materials from superatoms is a promising and versatile approach to create 2D materials with tunable physical and chemical properties.

Superatomic solid solutions.

In atomic solids, substitutional doping of atoms into the lattice of a material to form solid solutions is one of the most powerful approaches to modulating its properties and has led to the discovery of various metal alloys and semiconductors. Herein we have prepared solid solutions in hierarchical solids that are built from atomically precise clusters. Two geometrically similar metal chalcogenide clusters, Co6Se8(PEt3)6 and Cr6Te8(PEt3)6, were combined as random substitutional mixture, in three different ratios, in a crystal lattice together with fullerenes. This does not alter the underlying crystalline structure of the [cluster][C60]2 material, but it influences its electronic and magnetic properties. All three solid solutions showed increased electrical conductivities compared with either the Co- or Cr-based parent material, substantially so for two of the Co:Cr ratios (up to 100-fold), and lowered activation barriers for electron transport. We attribute this to the existence of additional energy states arising from the materials' structural heterogeneity, which effectively narrow transport gaps.

Precursor reaction kinetics control compositional grading and size of CdSe1-x S x nanocrystal heterostructures.

We report a method to control the composition and microstructure of CdSe1-x S x nanocrystals by the simultaneous injection of sulfide and selenide precursors into a solution of cadmium oleate and oleic acid at 240 °C. Pairs of substituted thio- and selenoureas were selected from a library of compounds with conversion reaction reactivity exponents (k E) spanning 1.3 × 10-5 s-1 to 2.0 × 10-1 s-1. Depending on the relative reactivity (k Se/k S), core/shell and alloyed architectures were obtained. Growth of a thick outer CdS shell using a syringe pump method provides gram quantities of brightly photoluminescent quantum dots (PLQY = 67 to 90%) in a single reaction vessel. Kinetics simulations predict that relative precursor reactivity ratios of less than 10 result in alloyed compositions, while larger reactivity differences lead to abrupt interfaces. CdSe1-x S x alloys (k Se/k S = 2.4) display two longitudinal optical phonon modes with composition dependent frequencies characteristic of the alloy microstructure. When one precursor is more reactive than the other, its conversion reactivity and mole fraction control the number of nuclei, the final nanocrystal size at full conversion, and the elemental composition. The utility of controlled reactivity for adjusting alloy microstructure is discussed.

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.

Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal.

The controlled introduction of impurities into the crystal lattice of solid-state compounds is a cornerstone of materials science. Intercalation, the insertion of guest atoms, ions or molecules between the atomic layers of a host structure, can produce novel electronic, magnetic and optical properties in many materials. Here we describe an intercalation compound in which the host [Co6Te8(PnPr3)6][C60]3, formed from the binary assembly of atomically precise molecular clusters, is a superatomic analogue of traditional layered atomic compounds. We find that tetracyanoethylene (TCNE) can be inserted into the superstructure through a single-crystal-to-single-crystal transformation. Using electronic absorption spectroscopy, electrical transport measurements and electronic structure calculations, we demonstrate that the intercalation is driven by the exchange of charge between the host [Co6Te8(PnPr3)6][C60]3 and the intercalant TCNE. These results show that intercalation is a powerful approach to manipulate the material properties of superatomic crystals.

Transition from Molecular Vibrations to Phonons in Atomically Precise Cadmium Selenide Quantum Dots.

We use micro-Raman spectroscopy to measure the vibrational structure of the atomically precise cadmium selenide quantum dots Cd35Se20X30L30, Cd56Se35X42L42, and Cd84Se56X56L56. These quantum dots have benzoate (X) and n-butylamine (L) ligands and tetrahedral (Td) shape with edges that range from 1.7 to 2.6 nm in length. Investigating this previously unexplored size regime allows us to identify the transition from molecular vibrations to bulk phonons in cadmium selenide quantum dots for the first time. Room-temperature Raman spectra have broad CdSe peaks at 175 and 200 cm-1. Density functional theory calculations assign these peaks to molecular surface and interior vibrational modes, respectively, and show that the interior, surface, and ligand atom motion is strongly coupled. The interior peak intensity increases relative to the surface peak as the cluster size increases due to the relative increase in the polarizability of interior modes with quantum dot size. The Raman spectra do not change with temperature for molecular Cd35Se20X30L30, while the interior peak narrows and shifts to higher energy as temperature decreases for Cd84Se56X56L56, a spectral evolution typical of a phonon. This result shows that the single bulk unit cell contained within Cd84Se56X56L56 is sufficient to apply a phonon confinement model, and that Cd56Se35X42L42, with its 2.1 nm edge length, marks the boundary between molecular vibrations and phonons.

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.

Ferromagnetic ordering in superatomic solids.

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.

Physical adsorption and charge transfer of molecular Br2 on graphene.

We present a detailed study of gaseous Br2 adsorption and charge transfer on graphene, combining in situ Raman spectroscopy and density functional theory (DFT). When graphene is encapsulated by hexagonal boron nitride (h-BN) layers on both sides, in a h-BN/graphene/h-BN sandwich structure, it is protected from doping by strongly oxidizing Br2. Graphene supported on only one side by h-BN shows strong hole doping by adsorbed Br2. Using Raman spectroscopy, we determine the graphene charge density as a function of pressure. DFT calculations reveal the variation in charge transfer per adsorbed molecule as a function of coverage. The molecular adsorption isotherm (coverage versus pressure) is obtained by combining Raman spectra with DFT calculations. The Fowler-Guggenheim isotherm fits better than the Langmuir isotherm. The fitting yields the adsorption equilibrium constant (∼0.31 Torr(-1)) and repulsive lateral interaction (∼20 meV) between adsorbed Br2 molecules. The Br2 molecule binding energy is ∼0.35 eV. We estimate that at monolayer coverage each Br2 molecule accepts 0.09 e- from single-layer graphene. If graphene is supported on SiO2 instead of h-BN, a threshold pressure is observed for diffusion of Br2 along the (somewhat rough) SiO2/graphene interface. At high pressure, graphene supported on SiO2 is doped by adsorbed Br2 on both sides.

Nanoscale atoms in solid-state chemistry.

We describe a solid-state material formed from binary assembly of atomically precise molecular clusters. [Co6Se8(PEt3)6][C60]2 and [Cr6Te8(PEt3)6][C60]2 assembled into a superatomic relative of the cadmium iodide (CdI2) structure type. These solid-state materials showed activated electronic transport with activation energies of 100 to 150 millielectron volts. The more reducing cluster Ni9Te6(PEt3)8 transferred more charge to the fullerene and formed a rock-salt-related structure. In this material, the constituent clusters are able to interact electronically to produce a magnetically ordered phase at low temperature, akin to atoms in a solid-state compound.

R6G on graphene: high Raman detection sensitivity, yet decreased Raman cross-section.

Several recent studies have demonstrated the use of single and few-layer graphene as a substrate for the enhancement of Raman scattering by adsorbed molecules in a method termed graphene-enhanced Raman spectroscopy (GERS). Here we determine the resonance Raman scattering cross-section for the dye molecule rhodamine 6G (R6G) adsorbed on bilayer graphene. For the 1650 cm(-1) R6G mode, we obtain a cross-section of 5.1 × 10(-24) cm(2)·molecule(-1), a greater than 3-fold reduction from the previously reported solution value. We show that the absorption spectrum of adsorbed R6G can be measured using micro-optical contrast spectroscopy, and we find that detuning of the molecular resonance explains the decreased Raman scattering cross-section. We find no evidence for a graphene Raman enhancement process. We also study the graphene thickness dependence of the adsorbed R6G Raman signal and show that a model incorporating electromagnetic interference effects can qualitatively explain the decrease in signal with increasing graphene thickness.

Strong charge-transfer doping of 1 to 10 layer graphene by NO2.

We use resonance Raman and optical reflection contrast methods to study charge transfer in 1-10 layer (1L-10L) thick graphene samples on which NO(2) has adsorbed. Electrons transfer from the graphene to NO(2), leaving the graphene layers doped with mobile delocalized holes. Doping follows a Langmuir-type isotherm as a function of NO(2) pressure. Raman and optical contrast spectra provide independent, self-consistent measures of the hole density and distribution as a function of the number of layers (N). At high doping, as the Fermi level shift E(F) reaches half the laser photon energy, a resonance in the graphene G mode Raman intensity is observed. We observe a decrease of graphene optical absorption in the near-IR that is due to hole-doping. Highly doped graphene is more optically transparent and much more electrically conductive than intrinsic graphene. In thicker samples, holes are effectively confined near the surface, and in these samples, a small band gap opens near the surface. We discuss the properties and versatility of these highly charge-transfer-doped, few-layer-thick graphene samples as a new class of electronic materials.

Optical reflectivity and Raman scattering in few-layer-thick graphene highly doped by K and Rb.

We report the optical reflectivity and Raman scattering of few layer (L) graphene exposed to K and Rb vapors. Samples many tens of layers thick show the reflectivity and Raman spectra of the stage 1 bulk alkali intercalation compounds (GICs) KC(8) and RbC(8). However, these bulk optical and Raman properties only begin to appear in samples more than about 15 graphene layers thick. The 1 L to 4 L alkali exposed graphene Raman spectra are profoundly different than the Breit-Wigner-Fano (BWF) spectra of the bulk stage 1 compounds. Samples less than 10 layers thick show Drude-like plasma edge reflectivity dip in the visible; alkali exposed few layer graphenes are significantly more transparent than intrinsic graphene. Simulations show the in-plane free electron density is lower than in the bulk stage 1 GICs. In few layer graphenes, alkalis both intercalate between layers and adsorb on the graphene surfaces. Charge transfer electrically dopes the graphene sheets to densities near and above 10(+14) electrons/cm(2). New intrinsic Raman modes at 1128 and 1264 cm(-1) are activated by in-plane graphene zone folding caused by strongly interacting, locally crystalline alkali adlayers. The K Raman spectra are independent of thickness for L = 1-4, indicating that charge transfer from adsorbed and intercalated K layers are similar. The Raman G mode is downshifted and significantly broadened from intrinsic graphene. In contrast, the Rb spectra vary strongly with L and show increased doping by intercalated alkali as L increases. Rb adlayers appear to be disordered liquids, while intercalated layers are locally crystalline solids. A significant intramolecular G mode electronic resonance Raman enhancement is observed in K exposed graphene, as compared with intrinsic graphene.

Raman enhancement on graphene: adsorbed and intercalated molecular species.

Strong Raman scattering is observed from iodine anions adsorbed at ca. 3% coverage on single layer graphene. In addition, the Raman signal from just one bromine intercalation layer inside three and four layer thick graphenes is observed. We analyze and model the intramolecular electronic, charge-transfer, and multiple reflection electromagnetic mechanisms responsible for this unusual sensitivity. Graphene is an excellent Raman substrate for adsorbed species showing intramolecular electronic resonance, because graphene efficiently quenches interfering excited-state luminescence. The Raman sensitivity for adsorbed and intercalated molecular species is highest for single layer graphene and decreases with increasing thickness. These phenomena are compared with surface enhanced Raman spectroscopy field enhancement and "chemical" Raman processes in aggregated Ag particles and on flat, highly reflective metal surfaces. The Raman spectra of adsorbed bromine layers are not observed, despite significant charge transfer to graphene. Charge transfer from adsorbed bromine is about one-half of charge transfer from intercalated bromine. We attribute the large Raman signal for both adsorbed iodine and intercalated bromine species to intramolecular electronic resonance enhancement. The signal evolution with varying graphene thickness is explained by multiple reflection electromagnetic calculations.

Ultrafast observation of isomerization and complexation in the photolysis of bromoform in solution.

Ultrafast photolysis of bromoform (CHBr(3)) with a 267 nm pulse of light followed by broadband transient electronic absorption identifies the photoproducts and follows their evolution in both neat bromoform and cyclohexane solutions. In neat bromoform, a species absorbing at 390 nm appears promptly and decays with a time constant of 13 ps as another species absorbing at 495 nm appears. The wavelength and time evolution of the first absorption is consistent with the formation of iso-bromoform (CHBr(2)-Br) by recombination of the fragment radicals within the solvent cage. The presence of an isosbestic point in the transient spectra indicates that this isomer is the precursor of the second absorber. The excess internal energy remaining in iso-bromoform permits release of the weakly bound Br atom to form a complex, CHBr(3)-Br, with other bromoform molecules. The features in the transient spectra are qualitatively similar in cyclohexane solutions of bromoform. The wavelength of the transition of iso-bromoform does not change upon dilution, but that of the CHBr(3)-Br complex systematically decreases with addition of cyclohexane. This trend agrees with the predicted dependence of the energy of a charge-transfer transition on the dielectric constant of the medium. Vibrational relaxation is likely to be the controlling feature of the evolution of the initially formed iso-bromoform.

Time-resolved studies of the reactions of CN radical complexes with alkanes, alcohols, and chloroalkanes.

Ultrafast transient absorption experiments monitor the reaction of CN radicals with 16 different alkane, alcohol, and chloroalkane solutes in CH(2)Cl(2) and with a smaller number of representative solutes in CHCl(3) and CH(3)CCl(3). In these experiments, 267-nm photolysis generates CN radicals, and transient electronic absorption at 400 nm probes their time evolution. A crucial feature of the reactions of CN radicals is their rapid formation of two different types of complexes with the solvent that have different stabilities and reactivities. The signature of the formation of these complexes is the CN transient absorption disappearing more slowly than the infrared transient absorption of the HCN product appears. Studying both the growth of HCN and the decay of the CN-solvent complexes in the reaction of CN with pentane in CH(2)Cl(2) and CHCl(3) solutions provides the information needed to build a kinetic model that accounts for the reaction of both complexes. This model permits analysis of the reaction of each of the 16 different solutes using only the decay of the CN transient absorption. The reaction of CN-solvent complexes with alkanes and chloroalkanes is slower than the corresponding reactions of Cl. However, the reactions of alcohols with both CN and Cl occur at about the same rate, likely reflecting additional complexation of the CN radical or its ICN precursor by the alcohol. The rates for the reactions of CN with the chloroalkanes decrease with increasing Cl content of the solute, in keeping with previous observations for the reactions of Cl in both gases and liquids.

Time-resolved studies of CN radical reactions and the role of complexes in solution.

Time-resolved studies using 100 fs laser pulses generate CN radicals photolytically in solution and probe their subsequent reaction with solvent molecules by monitoring both radical loss and product formation. The experiments follow the CN reactants by transient electronic spectroscopy at 400 nm and monitor the HCN products by transient vibrational spectroscopy near 3.07 microm. The observation that CN disappears more slowly than HCN appears shows that the two processes are decoupled kinetically and suggests that the CN radicals rapidly form two different types of complexes that have different reactivities. Electronic structure calculations find two bound complexes between CN and a typical solvent molecule (CH(2)Cl(2)) that are consistent with this picture. The more weakly bound complex is linear with CN bound to an H atom through the N atom, and the more strongly bound complex has a structure in which the CN bridges Cl and H atoms of the solvent. Fitting the transient absorption data with a kinetic model containing two uncoupled complexes reproduces the data for seven different chlorinated alkane solvents and yields rate constants for the reaction of each type of complex. Depending on the solvent, the linear complex reacts between 2.5 and 12 times faster than the bridging complex and is the primary source of the HCN reaction product. Increasing the Cl atom content of the solvents decreases the reaction rate for both complexes.

Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride.

The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,p-H2...I35,37Cl(X,v' '=0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D0' ' = 186.4(3) cm-1 versus 82.8(3)