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Showing papers in "Nature Chemistry in 2010"


Journal ArticleDOI
TL;DR: This Review highlights the recent advances in optical properties of chemically derived GO, as well as new physical and biological applications that are attracting chemists for its own characteristics.
Abstract: Chemically derived graphene oxide (GO) is an atomically thin sheet of graphite that has traditionally served as a precursor for graphene, but is increasingly attracting chemists for its own characteristics. It is covalently decorated with oxygen-containing functional groups - either on the basal plane or at the edges - so that it contains a mixture of sp(2)- and sp(3)-hybridized carbon atoms. In particular, manipulation of the size, shape and relative fraction of the sp(2)-hybridized domains of GO by reduction chemistry provides opportunities for tailoring its optoelectronic properties. For example, as-synthesized GO is insulating but controlled deoxidation leads to an electrically and optically active material that is transparent and conducting. Furthermore, in contrast to pure graphene, GO is fluorescent over a broad range of wavelengths, owing to its heterogeneous electronic structure. In this Review, we highlight the recent advances in optical properties of chemically derived GO, as well as new physical and biological applications.

2,937 citations


Journal ArticleDOI
TL;DR: It is shown how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries.
Abstract: Electrocatalysis will play a key role in future energy conversion and storage technologies, such as water electrolysers, fuel cells and metal-air batteries. Molecular interactions between chemical reactants and the catalytic surface control the activity and efficiency, and hence need to be optimized; however, generalized experimental strategies to do so are scarce. Here we show how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries. We demonstrate the core-shell structure of the catalyst and clarify the mechanistic origin of its activity. The platinum-rich shell exhibits compressive strain, which results in a shift of the electronic band structure of platinum and weakening chemisorption of oxygenated species. We combine synthesis, measurements and an understanding of strain from theory to generate a reactivity-strain relationship that provides guidelines for tuning electrocatalytic activity.

2,375 citations


Journal ArticleDOI
TL;DR: Transition metal photocatalysis represents a promising strategy towards the development of practical, scalable industrial processes with great environmental benefits.
Abstract: Light can be considered an ideal reagent for environmentally friendly, 'green' chemical synthesis; unlike many conventional reagents, light is non-toxic, generates no waste, and can be obtained from renewable sources. Nevertheless, the need for high-energy ultraviolet radiation in most organic photochemical processes has limited both the practicality and environmental benefits of photochemical synthesis on industrially relevant scales. This perspective describes recent approaches to the use of metal polypyridyl photocatalysts in synthetic organic transformations. Given the remarkable photophysical properties of these complexes, these new transformations, which use Ru(bpy)(3)(2+) and related photocatalysts, can be conducted using almost any source of visible light, including both store-bought fluorescent light bulbs and ambient sunlight. Transition metal photocatalysis thus represents a promising strategy towards the development of practical, scalable industrial processes with great environmental benefits.

2,036 citations


Journal ArticleDOI
TL;DR: The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene.
Abstract: The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed.

1,624 citations


Journal ArticleDOI
TL;DR: Computational modelling is used to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area that had high storage capacities for hydrogen and carbon dioxide and was in excellent agreement with predictions from modelling.
Abstract: Metal-organic frameworks--a class of porous hybrid materials built from metal ions and organic bridges--have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m(2) g(-1)). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g(-1)) and carbon dioxide (2,315 mg g(-1))--gases of high importance in the contexts of clean energy and climate alteration, respectively--in excellent agreement with predictions from modelling.

1,461 citations


Journal ArticleDOI
TL;DR: The first applications of asymmetric organocatalytic cascade reactions to the total synthesis of natural products are presented, paving the way for a new and powerful strategy that can help to address these issues.
Abstract: The total synthesis of natural products and biologically active compounds, such as pharmaceuticals and agrochemicals, has reached an extraordinary level of sophistication. We are, however, still far away from the 'ideal synthesis' and the state of the art is still frequently hampered by lengthy protecting-group strategies and costly purification procedures derived from the step-by-step protocols. In recent years several new criteria have been brought forward to solve these problems and to improve total synthesis: atom, step and redox economy or protecting-group-free synthesis. Over the past decade the research area of organocatalysis has rapidly grown to become a third pillar of asymmetric catalysis standing next to metal and biocatalysis, thus paving the way for a new and powerful strategy that can help to address these issues - organocatalytic cascade reactions. In this Review we present the first applications of such asymmetric organocascade reactions to the total synthesis of natural products.

1,315 citations


Journal ArticleDOI
TL;DR: Jean-Marie Tarascon ponders on the value of lithium, an element known for about 200 years, whose importance is now fast increasing in view of the promises it holds for energy storage and electric cars.
Abstract: Jean-Marie Tarascon ponders on the value of lithium, an element known for about 200 years, whose importance is now fast increasing in view of the promises it holds for energy storage and electric cars.

918 citations


Journal ArticleDOI
TL;DR: Aqueous lithium-ion batteries exhibited excellent stability with capacity retention over 90% after 1,000 cycles when being fully charged/discharged in 10 minutes and 85% after 50 cycles even at a very low current rate of 8 hours for a full charge/discharge offering an energy storage system with high safety, low cost, long cycling life and appropriate energy density.
Abstract: Aqueous lithium-ion batteries may solve the safety problem associated with lithium-ion batteries that use highly toxic and flammable organic solvents, and the poor cycling life associated with commercialized aqueous rechargeable batteries such as lead-acid and nickel-metal hydride systems. But all reported aqueous lithium-ion battery systems have shown poor stability: the capacity retention is typically less than 50% after 100 cycles. Here, the stability of electrode materials in an aqueous electrolyte was extensively analysed. The negative electrodes of aqueous lithium-ion batteries in a discharged state can react with water and oxygen, resulting in capacity fading upon cycling. By eliminating oxygen, adjusting the pH values of the electrolyte and using carbon-coated electrode materials, LiTi(2)(PO(4))(3)/Li(2)SO(4)/LiFePO(4) aqueous lithium-ion batteries exhibited excellent stability with capacity retention over 90% after 1,000 cycles when being fully charged/discharged in 10 minutes and 85% after 50 cycles even at a very low current rate of 8 hours for a full charge/discharge offering an energy storage system with high safety, low cost, long cycling life and appropriate energy density.

790 citations


Journal ArticleDOI
TL;DR: It is found that a member of the covalent organic framework family, COF-10, shows the highest uptake capacity of any porous material, including microporous 13X zeolite, Amberlyst 15, and mesoporous silica, MCM-41.
Abstract: Covalent organic frameworks (COFs) are porous crystalline materials composed of light elements linked by strong covalent bonds. A number of these materials contain a high density of Lewis acid boron sites that can strongly interact with Lewis basic guests, which makes them ideal for the storage of corrosive chemicals such as ammonia. We found that a member of the covalent organic framework family, COF-10, shows the highest uptake capacity (15 mol kg⁻¹, 298 K, 1 bar) of any porous material, including microporous 13X zeolite (9 mol kg⁻¹), Amberlyst 15 (11 mol kg⁻¹) and mesoporous silica, MCM-41 (7.9 mol kg⁻¹). Notably, ammonia can be removed from the pores of COF-10 by heating samples at 200°C under vacuum. In addition, repeated adsorption of ammonia into COF-10 causes a shift in the interlayer packing, which reduces its apparent surface area to nitrogen. However, owing to the strong Lewis acid-base interactions, the total uptake capacity of ammonia and the structural integrity of the COF are maintained after several cycles of adsorption/desorption.

781 citations


Journal ArticleDOI
TL;DR: This work demonstrates the systematic design of eight mesoporous chiral metal-organic frameworks, with the framework formula [LCu2(solvent)2] (where L is a chiral tetracarboxylate ligand derived from 1,1'-bi-2-naphthol), that have the same structures but channels of different sizes.
Abstract: A series of chiral metal–organic frameworks with channels of tunable size have been modified through post-synthetic functionalization to bear catalytic centres along their pore walls. The resulting materials catalyse a carbon–carbon-bond-forming reaction, and the enantioselectivity of the transformation can be altered by changing the size of the channels.

780 citations


Journal ArticleDOI
TL;DR: The application of the latest photonic quantum computer technology to calculate properties of the smallest molecular system: the hydrogen molecule in a minimal basis is reported and the complete energy spectrum is calculated to 20 bits of precision.
Abstract: Exact first-principles calculations of molecular properties are currently intractable because their computational cost grows exponentially with both the number of atoms and basis set size. A solution is to move to a radically different model of computing by building a quantum computer, which is a device that uses quantum systems themselves to store and process data. Here we report the application of the latest photonic quantum computer technology to calculate properties of the smallest molecular system: the hydrogen molecule in a minimal basis. We calculate the complete energy spectrum to 20 bits of precision and discuss how the technique can be expanded to solve large-scale chemical problems that lie beyond the reach of modern supercomputers. These results represent an early practical step toward a powerful tool with a broad range of quantum-chemical applications.

Journal ArticleDOI
TL;DR: A new Lewis acid-catalysed protocol to form boronate esters directly from protected catechols and arylboronic acids is reported, which provides crystalline bor onate ester-linked COFs from protected polyfunctional catechol and bis(boronic acid) linkers.
Abstract: Covalent organic frameworks (COFs) offer a new strategy for assembling organic semiconductors into robust networks with atomic precision and long-range order. General methods for COF synthesis will allow complex building blocks to be incorporated into these emerging materials. Here we report a new Lewis acid-catalysed protocol to form boronate esters directly from protected catechols and arylboronic acids. This transformation also provides crystalline boronate ester-linked COFs from protected polyfunctional catechols and bis(boronic acids). Using this method, we prepared a new COF that features a square lattice composed of phthalocyanine macrocycles joined by phenylene bis(boronic acid) linkers. The phthalocyanines stack in an eclipsed fashion within the COF to form 2.3 nm pores that run parallel to the stacked chromophores. The material's broad absorbance over the solar spectrum, potential for efficient charge transport through the stacked phthalocyanines, good thermal stability and the modular nature of COF synthesis, show strong promise for applications in organic photovoltaic devices.

Journal ArticleDOI
TL;DR: A cross-coupling between aryl halides and common arenes mediated by 1,10-phenanthroline as catalyst, in the presence of potassium tert-butoxide as base is described, opening a new window for achieving C–H activation without the need for transition metal catalysts.
Abstract: The direct functionalization of C-H bonds has drawn the attention of chemists for almost a century. C-H activation has mainly been achieved through four metal-mediated pathways: oxidative addition, electrophilic substitution, σ-bond metathesis and metal-associated carbene/nitrene/oxo insertion. However, the identification of methods that do not require transition-metal catalysts is important because methods involving such catalysts are often expensive. Another advantage would be that the requirement to remove metallic impurities from products could be avoided, an important issue in the synthesis of pharmaceutical compounds. Here, we describe the identification of a cross-coupling between aryl iodides/bromides and the C-H bonds of arenes that is mediated solely by the presence of 1,10-phenanthroline as catalyst in the presence of KOt-Bu as a base. This apparently transition-metal-free process provides a new strategy with which to achieve direct C-H functionalization.

Journal ArticleDOI
TL;DR: The application of supramolecular assembly to the more traditional transition metal catalysis and to small-molecule organocatalysis is discussed and how catalyst-substrate interactions can be tailored to direct substrates along particular reaction paths and selectivities are discussed.
Abstract: Supramolecular catalysis - the assembly of catalyst species by harnessing multiple weak intramolecular interactions - has, until recently, been dominated by enzyme-inspired approaches. Such approaches often attempt to create an enzyme-like 'active site' and have concentrated on reactions similar to those catalysed by enzymes themselves. Here, we discuss the application of supramolecular assembly to the more traditional transition metal catalysis and to small-molecule organocatalysis. The modularity of self-assembled multicomponent catalysts means that a relatively small pool of catalyst components can provide rapid access to a large number of catalysts that can be evaluated for industrially relevant reactions. In addition, we discuss how catalyst-substrate interactions can be tailored to direct substrates along particular reaction paths and selectivities.

Journal ArticleDOI
TL;DR: A synthetic strategy based on the substitution of bridging ligands in soluble metal-organic polyhedra with distinct properties is demonstrated.
Abstract: Metal-organic polyhedra-discrete molecular architectures constructed through the coordination of metal ions and organic linkers-have recently attracted considerable attention due to their intriguing structures, their potential for a variety of applications and their relevance to biological self-assembly. Several synthetic routes have been investigated to prepare these complexes. However, to date, these preparative methods have typically been based on the direct assembly of metal ions and organic linkers. Although these routes are convenient, it remains difficult to find suitable reaction conditions or to control the outcome of the assembly process. Here, we demonstrate a synthetic strategy based on the substitution of bridging ligands in soluble metal-organic polyhedra. The introduction of linkers with different properties from those of the initial metal-organic polyhedra can thus lead to new metal-organic polyhedra with distinct properties (including size and shape). Furthermore, partial substitution can also occur and form mixed-ligand species that may be difficult to access by means of other approaches.

Journal ArticleDOI
TL;DR: A novel, iodide-free redox electrolyte in conjunction with a sensitized heterojunction that has negligible absorption in the visible spectral range is presented, a very attractive feature for flexible DSCs that use transparent conductors as current collectors.
Abstract: Dye-sensitized solar cells (DSCs) have achieved impressive conversion efficiencies for solar energy of over 11% with an electrolyte that contains triiodide/iodide as a redox couple. Although triiodide/iodide redox couples work efficiently in DSCs, they suffer from two major disadvantages: electrolytes that contain triiodide/iodide corrode electrical contacts made of silver (which reduces the options for the scale up of DSCs to module size) and triiodide partially absorbs visible light. Here, we present a new disulfide/thiolate redox couple that has negligible absorption in the visible spectral range, a very attractive feature for flexible DSCs that use transparent conductors as current collectors. Using this novel, iodide-free redox electrolyte in conjunction with a sensitized heterojunction, we achieved an unprecedented efficiency of 6.4% under standard illumination test conditions. This novel redox couple offers a viable pathway to develop efficient DSCs with attractive properties for scale up and practical applications.

Journal ArticleDOI
TL;DR: This Review will consider recent progress and future potential in the development of methods for the preparation of chirally pure solids, in particular where the building blocks of the structure are achiral themselves.
Abstract: In many areas of chemistry the synthesis of chiral compounds is a target of increasing importance. They play a vital role in biological function and in many areas of society and science, including biology, medicine, biotechnology, chemistry and agriculture. Many pharmaceutical molecules, like their biological targets, are chiral and it is therefore easy to understand the growing demand for efficient methods of producing enantiomerically pure compounds. This is equally true for the preparation of chiral solids, which have potential applications in asymmetric catalysis, chiral separations and the like. In this Review we will consider recent progress and future potential in the development of methods for the preparation of chirally pure solids, in particular where the building blocks of the structure are achiral themselves. We will discuss strategies for the synthesis of both inorganic (for example, zeolites) and inorganic-organic hybrid (for example, metal organic framework) chiral porous solids.

Journal ArticleDOI
TL;DR: Initial cellular evaluations supports the view that compound collections based on natural-product-inspired scaffolds constructed with complex stereochemistry, and decorated with assorted substituents, will be a rich source of compounds with diverse bioactivity.
Abstract: A Lewis-acid-catalysed 1,3-dipolar cycloaddition provides rapid access to a variety of substituted spirooxindoles. Initial cellular evaluations supports the view that compound collections based on natural-product-inspired scaffolds constructed with complex stereochemistry, and decorated with assorted substituents, will be a rich source of compounds with diverse bioactivity.

Journal ArticleDOI
TL;DR: The controlled formation of highly monodisperse cylindrical block copolymer micelles is reported by the use of very small (approximately 20 nm) uniform crystallite seeds that serve as initiators for the crystallization-driven living self-assembly of added block-copolymer unimers with a crystallizable, core-forming metalloblock.
Abstract: Non-spherical nanostructures derived from soft matter and with uniform size-that is, monodisperse materials-are of particular utility and interest, but are very rare outside the biological domain. We report the controlled formation of highly monodisperse cylindrical block copolymer micelles (length dispersity < or = 1.03; length range, approximately 200 nm to 2 microm) by the use of very small (approximately 20 nm) uniform crystallite seeds that serve as initiators for the crystallization-driven living self-assembly of added block-copolymer unimers with a crystallizable, core-forming metalloblock. This process is analogous to the use of small initiator molecules in classical living polymerization reactions. The length of the nanocylinders could be precisely controlled by variation of the unimer-to-crystallite seed ratio. Samples of the highly monodisperse nanocylinders of different lengths that are accessible using this approach have been shown to exhibit distinct liquid-crystalline alignment behaviour.

Journal ArticleDOI
TL;DR: An investigation of the B₁₉⁻ cluster is reported, which shows chemical bonding reminiscent of that inannulene andcirculene, which possesses a unique double π-aromaticity in two concentric ρ-systems.
Abstract: A combined theoretical and experimental approach has been used to investigate the structure and bonding of an all-boron cluster (B19−). Calculations suggest that the minimum energy structure is a near-planar one — in which a pentagonal B6 unit is encircled by a larger B13 ring — possessing two concentric aromatic π systems.

Journal ArticleDOI
TL;DR: This work devised a gas phase chemical approach to etch graphene from the edges without damaging its basal plane and opens up a chemical way to control the size of various graphene nano-structures beyond the capability of top-down lithography.
Abstract: Large-scale graphene electronics requires lithographic patterning of narrow graphene nanoribbons for device integration. However, conventional lithography can only reliably pattern approximately 20-nm-wide GNR arrays limited by lithography resolution, while sub-5-nm GNRs are desirable for high on/off ratio field-effect transistors at room temperature. Here, we devised a gas phase chemical approach to etch graphene from the edges without damaging its basal plane. The reaction involved high temperature oxidation of graphene in a slightly reducing environment in the presence of ammonia to afford controlled etch rate (less than or approximately 1 nm min(-1)). We fabricated approximately 20-30-nm-wide graphene nanoribbon arrays lithographically, and used the gas phase etching chemistry to narrow the ribbons down to <10 nm. For the first time, a high on/off ratio up to approximately 10(4) was achieved at room temperature for field-effect transistors built with sub-5-nm-wide graphene nanoribbon semiconductors derived from lithographic patterning and narrowing. Our controlled etching method opens up a chemical way to control the size of various graphene nano-structures beyond the capability of top-down lithography.

Journal ArticleDOI
TL;DR: This work presents a simple and robust, chemically controlled process for synthesizing size-controlled noble metal or bimetallic nanocrystallites embedded within the porous structure of ordered mesoporous carbon (OMC).
Abstract: Shape- and size-controlled supported metal and intermetallic nanocrystallites are of increasing interest because of their catalytic and electrocatalytic properties. In particular, intermetallics PtX (X 5 Bi, Pb, Pd, Ru) are very attractive because of their high activity as fuel-cell anode catalysts for formic acid or methanol oxidation. These are normally synthesized using high-temperature techniques, but rigorous size control is very challenging. Even low-temperature techniques typically produce nanoparticles with dimensions much greater than the optimum <6 nm required for fuel cell catalysis. Here, we present a simple and robust, chemically controlled process for synthesizing size-controlled noble metal or bimetallic nanocrystallites embedded within the porous structure of ordered mesoporous carbon (OMC). By using surface-modified ordered mesoporous carbon to trap the metal precursors, nanocrystallites are formed with monodisperse sizes as low as 1.5 nm, which can be tuned up to ∼3.5 nm. To the best of our knowledge, 3-nm ordered mesoporous carbon-supported PtBi nanoparticles exhibit the highest mass activity for formic acid oxidation reported to date, and over double that of Pt–Au.

Journal ArticleDOI
TL;DR: The bioinspired electrode addresses the one major challenge of artificial photosynthesis, namely efficient water oxidation, which brings us closer to being able to power the planet with carbon-free fuels.
Abstract: Water is the renewable, bulk chemical that nature uses to enable carbohydrate production from carbon dioxide. The dream goal of energy research is to transpose this incredibly efficient process and make an artificial device whereby the catalytic splitting of water is finalized to give a continuous production of oxygen and hydrogen. Success in this task would guarantee the generation of hydrogen as a carbon-free fuel to satisfy our energy demands at no environmental cost. Here we show that very efficient and stable nanostructured, oxygen-evolving anodes are obtained by the assembly of an oxygen-evolving polyoxometalate cluster (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes. Our bioinspired electrode addresses the one major challenge of artificial photosynthesis, namely efficient water oxidation, which brings us closer to being able to power the planet with carbon-free fuels.

Journal ArticleDOI
TL;DR: This Review provides an overview of vacuum-deposited organic networks at metal surfaces, using intermolecular hydrogen bonding, metal-atom coordination and in situ polymerization.
Abstract: The formation of single-layer-thick molecular networks at metal surfaces is governed by the interplay between intermolecular and interfacial interactions. This Review highlights how, with films built by vacuum deposition, these interactions can be modulated to form substrates that may be useful as catalysts or templates for further deposition steps.

Journal ArticleDOI
TL;DR: It is concluded that anion-pi interactions on monomeric surfaces are ideal for chloride recognition, whereas their supramolecular enhancement by pi,pi-interactions appears perfect to target nitrate.
Abstract: Attractive in theory and confirmed to exist, anion–π interactions have never really been seen at work. To catch them in action, we prepared a collection of monomeric, cyclic and rod-shaped naphthalenediimide transporters. Their ability to exert anion–π interactions was demonstrated by electrospray tandem mass spectrometry in combination with theoretical calculations. To relate this structural evidence to transport activity in bilayer membranes, affinity and selectivity sequences were recorded. π-acidification and active-site decrowding increased binding, transport and chloride > bromide > iodide selectivity, and supramolecular organization inverted acetate > nitrate to nitrate > acetate selectivity. We conclude that anion–π interactions on monomeric surfaces are ideal for chloride recognition, whereas their supramolecular enhancement by π,π-interactions appears perfect to target nitrate. Chloride transporters are relevant to treat channelopathies, and nitrate sensors to monitor cellular signaling and cardiovascular diseases. A big impact on organocatalysis can be expected from the stabilization of anionic transition states on chiral π-acidic surfaces.

Journal ArticleDOI
TL;DR: This Perspective discusses recent developments with discrete organic molecules that are porous in the solid state and focuses on the possible advantages of organic molecules over inorganic or hybrid systems in terms of molecular solubility, choice of components and functionalities, and structural mobility and responsiveness in non-covalent extended solids.
Abstract: Most synthetic materials that show molecular-scale porosity consist of one-, two- or three-dimensional networks. Porous metal-organic frameworks in particular have attracted a lot of recent attention. By contrast, discrete molecules tend to pack efficiently in the solid state, leaving as little empty space as possible, which leads to non-porous materials. This Perspective discusses recent developments with discrete organic molecules that are porous in the solid state. Such molecules, which may be either crystalline or amorphous, can be categorized as either intrinsically porous (containing permanent covalent cavities) or extrinsically porous (inefficiently packed). We focus on the possible advantages of organic molecules over inorganic or hybrid systems in terms of molecular solubility, choice of components and functionalities, and structural mobility and responsiveness in non-covalent extended solids. We also highlight the potential for 'undiscovered' porous systems among the large number of cage-like organic molecules that are already known.

Journal ArticleDOI
TL;DR: A series of conjugated polyynes — the longest of which contains 44 contiguous acetylenic carbons — have been synthesized and their spectroscopic properties investigated.
Abstract: Carbyne is an allotrope of carbon composed of sp-hybridized carbon atoms. Although its formation in the laboratory is suggested, no well-defined sample is described. Interest in carbyne and its potential properties remains intense because of, at least in part, technological breakthroughs offered by other carbon allotropes, such as fullerenes, carbon nanotubes and graphene. Here, we describe the synthesis of a series of conjugated polyynes as models for carbyne. The longest of the series consists of 44 contiguous acetylenic carbons, and it maintains a framework clearly composed of alternating single and triple bonds. Spectroscopic analyses for these polyynes reveal a distinct trend towards a finite gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for carbyne, which is estimated to be ∼485 nm (∼2.56 eV). Even the longest members of this series of polyynes are not particularly sensitive to light, moisture or oxygen, and they can be handled and characterized under normal laboratory conditions.

Journal ArticleDOI
TL;DR: It is shown how a description of the local currents within a bridging molecule bound to metallic electrodes can provide chemical insight into current flow, and that interference effects can be characterized by the reversal of ring currents.
Abstract: A methodology for describing local electronic transmission through bridging molecules between metallic electrodes is presented. Its application to simple alkane, phenyl and cross-conjugated systems highlights an unexpected number of cases whereby ‘through space’, rather than ‘through bond’ terms dominate and that interference effects coincide with the reversal of ring currents.

Journal ArticleDOI
TL;DR: In this article, the authors used sophisticated ab initio calculations to show that singlet fission in pentacene proceeds through rapid internal conversion of the photoexcited state into a dark state of multi-exciton character that efficiently splits into two triplets.
Abstract: Multi-exciton generation-the creation of multiple charge carrier pairs from a single photon-has been reported for several materials and may dramatically increase solar cell efficiency. Singlet fission, its molecular analogue, may govern multi-exciton generation in a variety of materials, but a fundamental mechanism for singlet fission has yet to be described. Here, we use sophisticated ab initio calculations to show that singlet fission in pentacene proceeds through rapid internal conversion of the photoexcited state into a dark state of multi-exciton character that efficiently splits into two triplets. We show that singlet fission to produce a pair of triplet excitons must involve an intermediate state that (i) has a multi-exciton character, (ii) is energetically accessible from the optically allowed excited state, and (iii) efficiently dissociates into multiple electron-hole pairs. The rational design of photovoltaic materials that make use of singlet fission will require similar ab initio analysis of multi-exciton states such as the dark state studied here.

Journal ArticleDOI
TL;DR: The need to develop alternative catalysts for ammonia decomposition has been addressed here, using microkinetic modelling combined with density functional studies to identify suitable monolayer bimetallic catalysts based on nitrogen binding energies.
Abstract: The facile decomposition of ammonia to produce hydrogen is critical to its use as a hydrogen storage medium in a hydrogen economy, and although ruthenium shows good activity for catalysing this process, its expense and scarcity are prohibitive to large-scale commercialization. The need to develop alternative catalysts has been addressed here, using microkinetic modelling combined with density functional studies to identify suitable monolayer bimetallic (surface or subsurface) catalysts based on nitrogen binding energies. The Ni-Pt-Pt(111) surface, with one monolayer of Ni atoms residing on a Pt(111) substrate, was predicted to be a catalytically active surface. This was verified using temperature-programmed desorption and high-resolution electron energy loss spectroscopy experiments. The results reported here provide a framework for complex catalyst discovery. They also demonstrate the critical importance of combining theoretical and experimental approaches for identifying desirable monolayer bimetallic systems when the surface properties are not a linear function of the parent metals.