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Journal: Accounts of chemical research


This Account describes how attractive interactions of aromatic rings with other groups can influence and control the stereoselectivity of many reactions. Recent developments in theory have improved the accuracy in the modeling of aromatic interactions. Quantum mechanical modeling can now provide insights into the roles of these interactions at a level of detail not previously accessible, both for ground-state species and for transition states of chemical reactions. In this Account, we show how transition-state modeling led to the discovery of the influence of aryl groups on the stereoselectivities of several types of organic reactions, including asymmetric dihydroxylations, transfer hydrogenations, hetero-Diels-Alder reactions, acyl transfers, and Claisen rearrangements. Our recent studies have also led to a novel mechanistic picture for two classes of (4 + 3) cycloadditions, both of which involve reactions of furans with oxyallyl intermediates. The first class of cycloadditions, developed by Hsung, features neutral oxyallyl intermediates that contain a chiral oxazolidinone auxiliary. Originally, it was thought that these cycloadditions relied on differential steric crowding of the two faces of a planar intermediate. Computations reveal a different picture and show that cycloaddition with furan takes place preferentially through the more crowded transition state: the furan adds on the same side as the Ph substituent of the oxazolidinone. The crowded transition state is stabilized by a CH-π interaction between furan and Ph worth approximately 2 kcal/mol. Attractive interactions with aromatic rings also control the stereoselectivity in a second class of (4+3) cycloadditions involving chiral alkoxy siloxyallyl cations. Alkoxy groups derived from chiral α-methylbenzyl alcohols favor crowded transition states, where a stabilizing CH-π interaction is present between the furan and the Ar group. The cationic cycloadditions are stepwise, while the Hsung cycloadditions are concerted. Our results suggest that this form of CH- π-directed stereocontrol is quite general and likely controls the stereoselectivities of other addition reactions in which one face of a planar intermediate bears a pendant aromatic substituent.

Concepts: Chemical reaction, Transition state, Stereochemistry, Chemistry, Organic reaction, Transition state theory, Aromatic compounds, Thiophene


Porous coordination networks are materials that maintain their crystal structure as molecular “guests” enter and exit their pores. They are of great research interest with applications in areas such as catalysis, gas adsorption, proton conductivity, and drug release. As with zeolite preparation, the kinetic states in coordination network preparation play a crucial role in determining the final products. Controlling the kinetic state during self-assembly of coordination networks is a fundamental aspect of developing further functionalization of this class of materials. However, unlike for zeolites, there are few structural studies reporting the kinetic products made during self-assembly of coordination networks. Synthetic routes that produce the necessary selectivity are complex. The structural knowledge obtained from X-ray crystallography has been crucial for developing rational strategies for design of organic-inorganic hybrid networks. However, despite the explosive progress in the solid-state study of coordination networks during the last 15 years, researchers still do not understand many chemical reaction processes because of the difficulties in growing single crystals suitable for X-ray diffraction: Fast precipitation can lead to kinetic (metastable) products, but in microcrystalline form, unsuitable for single crystal X-ray analysis. X-ray powder diffraction (XRPD) routinely is used to check phase purity, crystallinity, and to monitor the stability of frameworks upon guest removal/inclusion under various conditions, but rarely is used for structure elucidation. Recent advances in structure determination of microcrystalline solids from ab initio XRPD have allowed three-dimensional structure determination when single crystals are not available. Thus, ab initio XRPD structure determination is becoming a powerful method for structure determination of microcrystalline solids, including porous coordination networks. Because of the great interest across scientific disciplines in coordination networks, especially porous coordination networks, the ability to determine crystal structures when the crystals are not suitable for single crystal X-ray analysis is of paramount importance. In this Account, we report the potential of kinetic control to synthesize new coordination networks and we describe ab initio XRPD structure determination to characterize these networks' crystal structures. We describe our recent work on selective instant synthesis to yield kinetically controlled porous coordination networks. We demonstrate that instant synthesis can selectively produce metastable networks that are not possible to synthesize by conventional solution chemistry. Using kinetic products, we provide mechanistic insights into thermally induced (573-723 K) (i.e., annealing method) structural transformations in porous coordination networks as well as examples of guest exchange/inclusion reactions. Finally, we describe a memory effect that allows the transfer of structural information from kinetic precursor structures to thermally stable structures through amorphous intermediate phases. We believe that ab initio XRPD structure determination will soon be used to investigate chemical processes that lead intrinsically to microcrystalline solids, which up to now have not been fully understood due to the unavailability of single crystals. For example, only recently have researchers used single-crystal X-ray diffraction to elucidate crystal-to-crystal chemical reactions taking place in the crystalline scaffold of coordination networks. The potential of ab initio X-ray powder diffraction analysis goes beyond single-crystal-to-single-crystal processes, potentially allowing members of this field to study intriguing in situ reactions, such as reactions within pores.

Concepts: Crystal, Diffraction, Crystallography, Chemistry, Solid, X-ray crystallography, Powder diffraction, Crystallographic database


Carbon nanotubes (CNTs) are carbon atoms arranged in a crystalline graphene lattice with a tubular morphology. CNTs exhibit high tensile strength, possess unique electrical properties, are durable, and can be functionalized. These properties allow applications as structural materials, in electronics, as heating elements, in batteries, in the production of stain-resistant fabric, for bone grafting and dental implants, and for targeted drug delivery. Carbon nanofibers (CNFs) are strong, flexible fibers that are currently used to produce composite materials. Agitation can lead to aerosolized CNTs and CNFs, and peak airborne particulate concentrations are associated with workplace activities such as weighing, transferring, mixing, blending, or sonication. Most airborne CNTs or CNFs found in workplaces are loose agglomerates of micrometer diameter. However, due to their low density, they linger in workplace air for a considerable time, and a large fraction of these structures are respirable. In rat and mouse models, pulmonary exposure to single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), or CNFs causes the following pulmonary reactions: acute pulmonary inflammation and injury, rapid and persistent formation of granulomatous lesions at deposition sites of large CNT agglomerates, and rapid and progressive alveolar interstitial fibrosis at deposition sites of more dispersed CNT or CNF structures. Pulmonary exposure to SWCNTs can induce oxidant stress in aortic tissue and increases plaque formation in an atherosclerotic mouse model. Pulmonary exposure to MWCNTs depresses the ability of coronary arterioles to respond to dilators. These cardiovascular effects may result from neurogenic signals from sensory irritant receptors in the lung. Pulmonary exposure to MWCNTs also upregulates mRNA for inflammatory mediators in selected brain regions, and pulmonary exposure to SWCNTs upregulates the baroreceptor reflex. In addition, pulmonary exposure to MWCNTs may induce levels of inflammatory mediators in the blood, which may affect the cardiovascular system. Intraperitoneal instillation of MWCNTs in mice has been associated with abdominal mesothelioma. MWCNTs deposited in the distal alveoli can migrate to the intrapleural space, and MWCNTs injected in the intrapleural space can cause lesions at the parietal pleura. However, further studies are required to determine whether pulmonary exposure to MWCNTs can induce pleural lesions or mesothelioma. In light of the anticipated growth in the production and use of CNTs and CNFs, worker exposure is possible. Because pulmonary exposure to CNTs and CNFs causes inflammatory and fibrotic reactions in the rodent lung, adverse health effects in workers represent a concern. NIOSH has conducted a risk assessment using available animal exposure-response data and is developing a recommended exposure limit for CNTs and CNFs. Evidence indicates that engineering controls and personal protective equipment can significantly decrease workplace exposure to CNTs and CNFs. Considering the available data on health risks, it appears prudent to develop prevention strategies to minimize workplace exposure. These strategies would include engineering controls (enclosure, exhaust ventilation), worker training, administrative controls, implementation of good handling practices, and the use of personal protective equipment (such as respirators) when necessary. NIOSH has published a document containing recommendations for the safe handling of nanomaterials.

Concepts: Heart, Carbon, Nanomaterials, Carbon nanotube, Graphite, Tensile strength, Pleural cavity, Parietal pleura


Graphene not only possesses interesting electrochemical behavior but also has a remarkable surface area and mechanical strength and is naturally abundant, all advantageous properties for the design of tailored composite materials. Graphene-semiconductor or -metal nanoparticle composites have the potential to function as efficient, multifunctional materials for energy conversion and storage. These next-generation composite systems could possess the capability to integrate conversion and storage of solar energy, detection, and selective destruction of trace environmental contaminants or achieve single-substrate, multistep heterogeneous catalysis. These advanced materials may soon become a reality, based on encouraging results in the key areas of energy conversion and sensing using graphene oxide as a support structure. Through recent advances, chemists can now integrate such processes on a single substrate while using synthetic designs that combine simplicity with a high degree of structural and composition selectivity. This progress represents the beginning of a transformative movement leveraging the advancements of single-purpose chemistry toward the creation of composites designed to address whole-process applications. The promising field of graphene nanocomposites for sensing and energy applications is based on fundamental studies that explain the electronic interactions between semiconductor or metal nanoparticles and graphene. In particular, reduced graphene oxide is a suitable composite substrate because of its two-dimensional structure, outstanding surface area, and electrical conductivity. In this Account, we describe common assembly methods for graphene composite materials and examine key studies that characterize its excited state interactions. We also discuss strategies to develop graphene composites and control electron capture and transport through the 2D carbon network. In addition, we provide a brief overview of advances in sensing, energy conversion, and storage applications that incorporate graphene-based composites. With these results in mind, we can envision a new class of semiconductor- or metal-graphene composites sensibly tailored to address the pressing need for advanced energy conversion and storage devices.

Concepts: Nanoparticle, Sun, Nanomaterials, Composite material, Solar energy, Solar power, Boeing 787, Carbon fiber


Concerns over global climate change associated with fossil-fuel consumption continue to drive the development of electrochemical alternatives for energy technology. Proton exchange fuel cells are a particularly promising technology for stationary power generation, mobile electronics, and hybrid engines in automobiles. For these devices to work efficiently, direct electrical contacts between the anode and cathode must be avoided; hence, the separator material must be electronically insulating but highly proton conductive. As a result, researchers have examined a variety of polymer electrolyte materials for use as membranes in these systems. In the optimization of the membrane, researchers are seeking high proton conductivity, low electronic conduction, and mechanical stability with the inclusion of water in the polymer matrix. A considerable number of potential polymer backbone and side chain combinations have been synthesized to meet these requirements, and computational studies can assist in the challenge of designing the next generation of technologically relevant membranes. Such studies can also be integrated in a feedback loop with experiment to improve fuel cell performance. However, to accurately simulate the currently favored class of membranes, perfluorosulfonic acid containing moieties, several difficulties must be addressed including a proper treatment of the proton-hopping mechanism through the membrane and the formation of nanophase-separated water networks. We discuss our recent efforts to address these difficulties using methods that push the limits of computer simulation and expand on previous theoretical developments. We describe recent advances in the multistate empirical valence bond (MS-EVB) method that can probe proton diffusion at the nanometer-length scale and accurately model the so-called Grotthuss shuttling mechanism for proton diffusion in water. Using both classical molecular dynamics and coarse-grained descriptions that replace atomistic representations with collective coordinates, we investigated the proton conductivity of polymer membrane structure as a function of hydration level. Nanometer-sized water channels form torturous pathways that are traversed by the charges during fuel cell operation. Using a combination of coarse-grained membrane structure and novel multiscale methods, we demonstrate emerging approaches to treat proton motion at the mesoscale in these complex materials.

Concepts: Cathode, Cell membrane, Electrochemistry, Battery, Electrolyte, Electrolysis, Anode, Proton exchange membrane fuel cell


Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters. In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF structures tend to have high hydrophilicity and guest-accessible voids, and scientists have reported many water-mediated proton (H(+)) conductivities. Chemical modification of organic ligands can change the hydrated H(+) conductivity over a wide range. On the other hand, the designable structures also permit water-free (anhydrous) H(+) conductivity. The incorporation of protic guests such as imidazole and 1,2,4-triazole into the microchannels of PCP/MOFs promotes the dynamic motion of guest molecules, resulting in high H(+) conduction without water. Not only the host-guest systems, but the embedding of protic organic groups on CPs also results in inherent H(+) conductivity. We have observed high H(+) conductivities under anhydrous conditions and in the intermediate temperature region of organic and inorganic conductors. The keys to successful construction are highly mobile ionic species and appropriate intervals of ion-hopping sites in the structures. Lithium (Li(+)) and other ions can also be transported. If we can optimize the crystal structures, this could offer further improvements in terms of both conductivity and the working temperature range. Another useful characteristic of PCP/MOFs is their wide application to materials fabrication. We can easily prepare heterodomain crystal systems, such as core-shell or solid solution. Other anisotropic morphologies (thin film, nanocrystal, nanorod, etc.,) are also possible, with retention of the ion conductivity. The flexible nature also lets us design morphology-dependent ion-conduction behaviors that we cannot observe in the bulk state. We propose (1) multivalent ion and anion conductions with the aid of redox activity and defects in structures, (2) control of ion transport behavior by applying external stimuli, (3) anomalous conductivity at the hetero-solid-solid interface, and (4) unidirectional ion transport as in the ion channels in membrane proteins. In the future, scientists may use coordination polymers not only to achieve higher conductivity but also to control ion behavior, which will open new avenues in solid-state ionics.

Concepts: Ammonia, Hydrogen, Chemistry, Ion, Solid, Sodium, Inorganic chemistry, Ionic bond


During carrier multiplication (CM), also known as multiexciton generation (MEG), absorption of a single photon produces multiple electron-hole pairs, or excitons. This process can appreciably increase the efficiency of photoconversion, which is especially beneficial in photocatalysis and photovoltaics. This Account reviews recent progress in understanding the CM process in semiconductor nanocrystals (NCs), motivated by the challenge researchers face to quickly identify candidate nanomaterials with enhanced CM. We present a possible solution to this problem by showing that, using measured biexciton Auger lifetimes and intraband relaxation rates as surrogates for, respectively, CM time constants and non-CM energy-loss rates, we can predict relative changes in CM yields as a function of composition. Indeed, by studying PbS, PbSe, and PbTe NCs of a variety of sizes we determine that the significant difference in CM yields for these compounds comes from the dissimilarities in their non-CM relaxation channels, i.e., the processes that compete with CM. This finding is likely general, as previous observations of a material-independent, “universal” volume-scaling of Auger lifetimes suggest that the timescale of the CM process itself is only weakly affected by NC composition. We further explore the role of nanostructure shape in the CM process. We observe that a moderate elongation (aspect ratio of 6-7) of PbSe NCs can cause up to an approximately two-fold increase in the multiexciton yield compared to spherical nanoparticles. The increased Auger lifetimes and improved charge transport properties generally associated with elongated nanostructures suggest that lead chalcogenide nanorods are a promising system for testing CM concepts in practical photovoltaics. Historically, experimental considerations have been an important factor influencing CM studies. To this end, we discuss the role of NC photocharging in CM measurements. Photocharging can distort multiexciton dynamics, leading to erroneous estimations of the CM yield. Here, we show that in addition to distorting time-resolved CM signals, photocharging also creates spectral signatures that mimic CM. This re-emphasizes the importance of a careful analysis of the potential effect of charged species in both optical and photocurrent-based measurements of this process.

Concepts: Addition, Nanotechnology, Nanomaterials, Semiconductor, Aspect ratio, Yield, Distortion, Multiplication


The recent re-emergence of the halide perovskites, of the type AMX3, derives from a sea-changing breakthrough in the field of photovoltaics that has led to a whole new generation of solar devices with remarkable power conversion efficiency. The success in the field of photovoltaics has led to intense, combined research efforts to better understand these materials both from the fundamental chemistry and physics points of view and for the improvement of applied functional device engineering. This groundswell of activity has breathed new life into this long-known but largely “forgotten” class of perovskites. The impressive achievements of halide perovskites in photovoltaics, as well as other optoelectronic applications, stem from an unusually favorable combination of optical and electronic properties, with the ability to be solution processed into films. This defines them as a brand new class of semiconductors that can rival or exceed the performance of the venerable classes of III-V and II-IV semiconductors, which presently dominate the industries of applied optoelectronics. Our aim in this Account is to highlight the basic pillars that define the chemistry of the halide perovskites and their unconventional electronic properties through the prism of structure-property relationships. We focus on the synthetic requirements under which a halide perovskite can exist and emphasize how the synthetic conditions can determine the structural integrity and the bulk properties of the perovskites. Then we proceed to discuss the origins of the optical and electronic phenomena, using the perovskite crystal structure as a guide. Some of the most remarkable features of the perovskites dealt with in this Account include the evolution of a unique type of defect, which gives rise to superlattices. These can enhance or diminish the fluorescence properties of the perovskites. For example, the exotic self-doping ability of the Sn-based perovskites allows them to adopt electrical properties from semiconducting to metallic. We attempt to rationalize how these properties can be tuned and partially controlled through targeted synthetic procedures for use in electronic and optical devices. In addition, we address open scientific questions that pose big obstacles in understanding the fundamentals of perovskites. We anticipate that the answers to these questions will provide the impetus upon which future research directions will be founded.

Concepts: Crystal structure, Semiconductor, Solar cell, Photovoltaics, Diode, Perovskite, Mineralogy, Optoelectronics


Organic-inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. High-efficiency solar cells can be produced with solution-processed active layers. The materials are earth abundant, and the simple processing required suggests that high-throughput and low-cost manufacture at scale should be possible. While these materials bear considerable similarity to traditional inorganic semiconductors, there are notable differences in their optoelectronic behavior. A key distinction of these materials is that they are physically soft, leading to considerable thermally activated motion. In this Account, we discuss the internal motion of methylammonium lead iodide (CH3NH3PbI3) and formamidinium lead iodide ([CH(NH2)2]PbI3), covering: (i) molecular rotation-libration in the cuboctahedral cavity; (ii) drift and diffusion of large electron and hole polarons; (iii) transport of charged ionic defects. These processes give rise to a range of properties that are unconventional for photovoltaic materials, including frequency-dependent permittivity, low electron-hole recombination rates, and current-voltage hysteresis. Multiscale simulations, drawing from electronic structure, ab initio molecular dynamic and Monte Carlo computational techniques, have been combined with neutron diffraction measurements, quasi-elastic neutron scattering, and ultrafast vibrational spectroscopy to qualify the nature and time scales of the motions. Electron and hole motion occurs on a femtosecond time scale. Molecular libration is a sub-picosecond process. Molecular rotations occur with a time constant of several picoseconds depending on the cation. Recent experimental evidence and theoretical models for simultaneous electron and ion transport in these materials has been presented, suggesting they are mixed-mode conductors with similarities to fast-ion conducting metal oxide perovskites developed for battery and fuel cell applications. We expound on the implications of these effects for the photovoltaic action. The temporal behavior displayed by hybrid perovskites introduces a sensitivity in materials characterization to the time and length scale of the measurement, as well as the history of each sample. It also poses significant challenges for accurate materials modeling and device simulations. There are large differences between the average and local crystal structures, and the nature of charge transport is too complex to be described by common one-dimensional drift-diffusion models. Herein, we critically discuss the atomistic origin of the dynamic processes and the associated chemical disorder intrinsic to crystalline hybrid perovskite semiconductors.

Concepts: Electron, Electric charge, Crystal, Ion, Semiconductor, Materials science, Solar cell, Photovoltaics


Mercury (Hg) is a global environmental contaminant. Major anthropogenic sources of Hg emission include gold mining and the burning of fossil fuels. Once deposited in aquatic environments, Hg can undergo redox reactions, form complexes with ligands, and adsorb onto particles. It can also be methylated by microorganisms. Mercury, especially its methylated form methylmercury, can be taken up by organisms, where it bioaccumulates and biomagnifies in the food chain, leading to detrimental effects on ecosystem and human health. In support of the recently enforced Minamata Convention on Mercury, a legally binding international convention aimed at reducing the anthropogenic emission of-and human exposure to-Hg, its global biogeochemical cycle must be understood. Thus, a detailed understanding of the molecular-level interactions of Hg is crucial. The ongoing rapid development of hardware and methods has brought computational chemistry to a point that it can usefully inform environmental science. This is particularly true for Hg, which is difficult to handle experimentally due to its ultratrace concentrations in the environment and its toxicity. The current account provides a synopsis of the application of computational chemistry to filling several major knowledge gaps in environmental Hg chemistry that have not been adequately addressed experimentally. Environmental Hg chemistry requires defining the factors that determine the relative affinities of different ligands for Hg species, as they are critical for understanding its speciation, transformation and bioaccumulation in the environment. Formation constants and the nature of bonding have been determined computationally for environmentally relevant Hg(II) complexes such as chlorides, hydroxides, sulfides and selenides, in various physical phases. Quantum chemistry has been used to determine the driving forces behind the speciation of Hg with hydrochalcogenide and halide ligands. Of particular importance is the detailed characterization of solvation effects. Indeed, the aqueous phase reverses trends in affinities found computationally in the gas phase. Computation has also been used to investigate complexes of methylmercury with (seleno)amino acids, providing a molecular-level understanding of the toxicological antagonism between Hg and selenium (Se). Furthermore, evidence is emerging that ice surfaces play an important role in Hg transport and transformation in polar and alpine regions. Therefore, the diffusion of Hg and its ions through an idealized ice surface has been characterized. Microorganisms are major players in environmental mercury cycling. Some methylate inorganic Hg species, whereas others demethylate methylmercury. Quantum chemistry has been used to investigate catalytic mechanisms of enzymatic Hg methylation and demethylation. The complex interplay between the myriad chemical reactions and transport properties both in and outside microbial cells determines net biogeochemical cycling. Prospects for scaling up molecular work to obtain a mechanistic understanding of Hg cycling with comprehensive multiscale biogeochemical modeling are also discussed.