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| Open AccessDynamic structural evolution of supported palladium–ceria core–shell catalysts revealed by in situ electron microscopy
There is currently renewed interest in the use of core–shell catalysts for methane combustion. Here, the authors perform anex situ and in situelectron microscopy study to probe the structural evolution of palladium–cerium dioxide catalytic core–shell subunits over a wide temperature range.
- Shuyi Zhang
- , Chen Chen
- & Xiaoqing Pan
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Article
| Open AccessHigh-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization
Hybrid perovskites are a promising class of materials for photovoltaic applications. Here, addressing the need for high-quality hybrid perovskite materials, the authors achieve the rapid growth of hybrid perovskite single crystals of high quality by inverse temperature crystallization.
- Makhsud I. Saidaminov
- , Ahmed L. Abdelhady
- & Osman M. Bakr
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Article
| Open AccessEdge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production
Layered molybdenum disulfide is a promising hydrogen evolution catalyst. Here, the authors report a strategy for synthesizing molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing and demonstrate their enhanced catalytic activity.
- Min-Rui Gao
- , Maria K.Y. Chan
- & Yugang Sun
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Article
| Open AccessUltrathin inorganic molecular nanowire based on polyoxometalates
Molecular nanowires, one-dimensional materials grown by repeating a molecular unit along a single axis, are fundamentally and technologically interesting materials. Here, the authors report a rare inorganic molecular nanowire comprised of polyoxometalates, and study its catalytic and electronic properties.
- Zhenxin Zhang
- , Toru Murayama
- & Wataru Ueda
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| Open AccessMixing of immiscible polymers using nanoporous coordination templates
The intimate mixing of immiscible polymers is desirable both to aid understanding of the fundamental science and for the development of new materials. Here, the authors successfully compatibilize polystyrene and poly(methyl methacrylate) using a porous coordination polymer as a removable template.
- Takashi Uemura
- , Tetsuya Kaseda
- & Susumu Kitagawa
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| Open AccessInfluencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands
Ligand design contributes to dictating the magnetic properties of lanthanide-based single-molecule magnets. Here, the authors report a series of phosphorus-ligated dysprosium complexes, and show that the dynamic magnetic properties change as the ligand is varied from phosphine to phosphide to phosphinidene.
- Thomas Pugh
- , Floriana Tuna
- & Richard A. Layfield
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Article
| Open AccessDecarbonylative organoboron cross-coupling of esters by nickel catalysis
The Suzuki-Miyaura cross-coupling is a mainstay of organic synthesis, allowing carbon-carbon bond formation between a variety of coupling partners. Here, the authors report a decarbonylative process, whereby alkyl or aryl esters can be coupled with organoboron compounds using nickel catalysts.
- Kei Muto
- , Junichiro Yamaguchi
- & Kenichiro Itami
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| Open AccessSingle-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol
Copper-exchanged zeolites with mordenite structure can mimic the active sites in particulate methane monooxygenase. Here, the authors show that mordenite micropores can stabilize trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane.
- Sebastian Grundner
- , Monica A.C. Markovits
- & Johannes A. Lercher
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| Open AccessKumada–Grignard-type biaryl couplings on water
Organomagnesium reagents have been a staple for carbon–carbon bond formations for over a century, but are notoriously sensitive to water. Here, the authors show a Kumada-type coupling of aryl halides on water, with a potential intermediary of an in situformed Grignard reagent.
- Anish Bhattacharjya
- , Piyatida Klumphu
- & Bruce H. Lipshutz
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| Open AccessParts-per-million level loading organocatalysed enantioselective silylation of alcohols
Organocatalytic methods typically do not approach the extremely low loadings that can be achieved with some metal catalysed processes. Here, the authors report a remarkably powerful organocatalyst capable of performing asymmetric silylations with sub parts-per-million level loadings.
- Sang Yeon Park
- , Ji-Woong Lee
- & Choong Eui Song
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| Open AccessRhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation
Fluoroalkenes are found widely in biologically active compounds, but their introduction can be difficult or laborious. Here, the authors report a C–H/C–F activation strategy to introduce monofluoroalkenes into organic molecules in one step with good to excellent yields.
- Panpan Tian
- , Chao Feng
- & Teck-Peng Loh
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Article
| Open AccessIn situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion
Palladium is an effective but expensive catalyst used in catalytic converters. Here, the authors show that defective Co3O4nanocrystals, synthesized via oxidation of carbon-encapsulated cobalt nanoparticles, display similar or even comparable catalytic activity to palladium for hydrocarbon combustion.
- Han Wang
- , Chunlin Chen
- & Jian Zhang
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Article
| Open AccessMicroporous metal–organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures
The removal of acetylene from ethylene/acetylene mixtures is an industrially important but challenging task. Here the authors report a microporous metal–organic framework with optimized pore/cage space design and chemical functionalization, capable of removing acetylene from low concentration mixtures.
- Tong-Liang Hu
- , Hailong Wang
- & Banglin Chen
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| Open AccessSpatially and temporally resolved gas distributions around heterogeneous catalysts using infrared planar laser-induced fluorescence
Visualization of the gas distribution around working catalyst is crucial for understanding structure–activity relationships. Here, the authors show that gas distribution can be imaged in situwith high spatial and temporal resolution using infrared planar laser-induced fluorescence.
- Johan Zetterberg
- , Sara Blomberg
- & Edvin Lundgren
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Article
| Open AccessTwo-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds
There is interest in the study of two-dimensional materials for catalysis. Here, the authors report the fabrication of two-dimensional gold nanostructures, using a layered double hydroxide as a stabilizing template, and evaluate the catalytic performance of the composite for solvent free selective oxidation.
- Liang Wang
- , Yihan Zhu
- & Feng-Shou Xiao
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Unique distal size selectivity with a digold catalyst during alkyne homocoupling
Steric hindrance proximal to a metal centre is known to play a key role in reactivity during catalysis. Here, the authors study reductive elimination from gold metal centres, surprisingly showing that small changes in sterics at sites removed from the metal centre can have dramatic effects on reactivity.
- Antonio Leyva-Pérez
- , Antonio Doménech-Carbó
- & Avelino Corma
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| Open AccessAn allosteric photoredox catalyst inspired by photosynthetic machinery
Photosynthetic systems regulate light harvesting via structural and electronic control of antenna proteins. Here, the authors report a light-harvesting antenna/reaction centre mimic that can be allosterically regulated using mild and redox-inactive inputs, via a coordination framework with hemilabile ligands.
- Alejo M. Lifschitz
- , Ryan M. Young
- & Chad A. Mirkin
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| Open AccessElectride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis
Development of catalysts that enhance dissociation of the nitrogen–nitrogen triple bond will reduce costs of ammonia production. Here, the authors study ammonia synthesis over a ruthenium loaded electride catalyst and show that the rate-determining step is shifted to nitrogen–hydrogen bond formation.
- Masaaki Kitano
- , Shinji Kanbara
- & Hideo Hosono
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| Open AccessDynamic control of chirality in phosphine ligands for enantioselective catalysis
Typically in asymmetric catalysis each product enantiomer is produced using a different enantiomer of catalyst. Here, the authors show a photoswitchable bisphosphine ligand, capable of altering the stereoselectivity of a palladium catalysed process and producing either enantiomer of product.
- Depeng Zhao
- , Thomas M. Neubauer
- & Ben L. Feringa
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| Open AccessElectrochemical synthesis of mesoporous gold films toward mesospace-stimulated optical properties
The selective growth of mesoporous gold thin films with control over the porosity is a challenging task. Here, the authors report a soft-templating method allowing the growth of tunable, mesoporous gold films and examine their optical properties
- Cuiling Li
- , Ömer Dag
- & Yusuke Yamauchi
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In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework
Ball milling chemical reactions are of interest due to their environmental credentials and potential to achieve new reactions and materials. Here, the authors isolate a metastable material with a previously unknown net topology by in situmonitoring of the mechanosynthesis of a metal organic framework.
- Athanassios D. Katsenis
- , Andreas Puškarić
- & Tomislav Friščić
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| Open AccessPorous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production
There is extensive research into non-platinum electrocatalysts for hydrogen evolution. Here, the authors report a molybdenum carbide catalyst, prepared via the carburization of a copper metal-organic framework host/molybdenum-based polyoxometalates guest system, and demonstrate its catalytic activity.
- Hao Bin Wu
- , Bao Yu Xia
- & Xiong Wen (David) Lou
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Article
| Open AccessA molecular catalyst for water oxidation that binds to metal oxide surfaces
Molecular catalysts can exhibit high activity, but their practical application may be limited by solubility and stability issues. Here, the authors report stable, direct binding of an iridium molecular catalyst to conductive oxide surfaces and demonstrate its activity for electrochemical water oxidation.
- Stafford W. Sheehan
- , Julianne M. Thomsen
- & Charles A. Schmuttenmaer
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| Open AccessCobalt-catalysed site-selective intra- and intermolecular dehydrogenative amination of unactivated sp3 carbons
Functionalizing unactivated carbon–hydrogen bonds is challenging, especially when using non-precious metals and dealing with sp3 hybridized carbons. Here, the authors report an intramolecular cobalt catalysed amination of C–H bonds of sp3carbons, giving access to β- and γ-lactams.
- Xuesong Wu
- , Ke Yang
- & Haibo Ge
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Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water
Coupling between alkyl halides and alkynes is commonly performed via the Sonogoshira reaction or variants thereof, but unactivated tertiary alkyl halides have proven to be elusive partners. Here, the authors report the metal-free coupling of tertiary alkyl halides and terminal alkynes taking place in water.
- Wenbo Liu
- , Lu Li
- & Chao-Jun Li
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Chiral recognition and selection during the self-assembly process of protein-mimic macroanions
Certain chiral macroions have previously been shown to self-assemble into spherical structures. Here, the authors observe self-sorting of racemic macroions into enantiomeric ‘blackberry’-shaped structures, and furthermore show that the addition of chiral co-anions allows the formation of a single enantiomer.
- Panchao Yin
- , Zhi-Ming Zhang
- & Tianbo Liu
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| Open AccessDynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles
Computational investigation of heterogeneous catalytic systems is fundamentally important. Here, the authors show that, under reaction conditions, reactant-induced structural changes in ceria-supported gold nanoparticle catalysts lead to the dynamic formation of single-atom catalytic sites at the interface.
- Yang-Gang Wang
- , Donghai Mei
- & Roger Rousseau
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Article
| Open AccessMolecular magnetic switch for a metallofullerene
Endohedral fullerenes are known to stabilize reactive radicals; however, the external magnetic manipulation of these species’ remains challenging. Here, the authors link a nitroxide radical to a paramagnetic fullerene system and are able to alter the spin behaviour of the fullerene via spin–spin interactions.
- Bo Wu
- , Taishan Wang
- & Chunru Wang
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A multicentre-bonded [ZnI]8 cluster with cubic aromaticity
Zinc(I) bimetallic clusters have previously been reported, but they are not stable in air. Here, the authors synthesize octametallic Zinc(I) clusters with multi-centred zinc–zinc bonds and extensive electron delocalization over the cluster, resulting in cubic aromaticity and enhanced stability.
- Ping Cui
- , Han-Shi Hu
- & Jun Li
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Self-catalysed aerobic oxidization of organic linker in porous crystal for on-demand regulation of sorption behaviours
Controlling and selectively altering the structure of materials opens up the possibility of modulating their physical properties. Here, the authors report a method for altering the properties of a coordination polymer, where the metal centres active molecular oxygen to oxidize the organic ligand.
- Pei-Qin Liao
- , Ai-Xin Zhu
- & Xiao-Ming Chen
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Article
| Open AccessCarbon–carbon bond activation of cyclobutenones enabled by the addition of chiral organocatalyst to ketone
Activation of C–C bonds is a powerful method for directly functionalizing organic molecules, but is still a challenging task. Here, the authors show that N-heterocyclic carbenes can activate the C–C bonds in cyclic ketones, allowing the enantioselective formation of lactams.
- Bao-Sheng Li
- , Yuhuang Wang
- & Yonggui Robin Chi
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Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation
Non-haeme iron complexes are known to be competent catalysts for chemically driven water oxidation. Here, the authors provide evidence for the formation of an inner-sphere iron(IV)- oxygen-cerium(IV) intermediate that may provide mechanistic insight into the naturally occurring oxygen evolving complex.
- Zoel Codolà
- , Laura Gómez
- & Julio Lloret-Fillol
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| Open AccessAn efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation
There is substantial research into new catalysts for electroreduction of water. Here, the authors report a robust and active molybdenum disulfide/cobalt diselenide hydrogen evolution catalyst with onset potential of 11 mV and Tafel slope of 36 mV per decade, approaching the activity of platinum.
- Min-Rui Gao
- , Jin-Xia Liang
- & Shu-Hong Yu
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Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2
Copolymers are the combination of two or more different monomers, often alternating in defined patterns. Here, the authors show a gradient copolymerization of two monomers with different crystalline properties, giving polymers where the crystallinity varies throughout the length of the chain.
- Ye Liu
- , Wei-Min Ren
- & Xiao-Bing Lu
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Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina
There has been a great deal of interest in single-atom heterogeneous catalysis recently. Here, the authors show that industrially relevant lanthanum oxide-doped alumina supports are capable of stabilizing atomically dispersed palladium species, which are evaluated for low-temperature carbon monoxide oxidation.
- Eric J. Peterson
- , Andrew T. DeLaRiva
- & Abhaya K. Datye
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Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite
The thermosalient effect is the unusual tendency of some crystals to visibly jump during phase changes. Here, the authors study the multiple phase changes in a prototypic thermosalient material and provide evidence for the factors that drive this self-actuation.
- Manas K. Panda
- , Tomče Runčevski
- & Panče Naumov
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Metal-templated chiral Brønsted base organocatalysis
Octahedral chiral-at-metal complexes have chirality based on the metal centre, but reactivity occurs at the organic ligands. Here, the authors report such a complex as a highly active Brønsted base catalyst, with loadings down to 0.02 mol% for asymmetric Michael additions and 0.25 mol% for aza-Henry reactions.
- Jiajia Ma
- , Xiaobing Ding
- & Eric Meggers
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Intramolecular C–F and C–H bond cleavage promoted by butadienyl heavy Grignard reagents
Grignard reagents are one of the mainstays of organic synthesis, but analogues with other Group 2 metals (heavy Grignards) are less easy to control. Here, the authors generate butadienyl calcium and barium heavy Grignards and control their reactivity in C–F and C–H cleavage reactions.
- Heng Li
- , Xiao-Ye Wang
- & Zhenfeng Xi
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Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis
Two-electron redox cycles are the basis for much of the synthetic utility of noble metals in organic chemistry, but these mechanisms have not been explored for silver. Here, the authors show a silver(I)/silver(III) catalytic cycle operating in cross-coupling reactions.
- Marc Font
- , Ferran Acuña-Parés
- & Xavi Ribas
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Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction
Lithium cobalt oxide is widely studied for electrocatalytic applications. Here, the authors develop a technique for delithiating the material in organic electrolyte, and demonstrate that the oxygen evolution catalytic activity is significantly improved after the treatment.
- Zhiyi Lu
- , Haotian Wang
- & Yi Cui
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Article
| Open AccessDiscovery of gigantic molecular nanostructures using a flow reaction array as a search engine
The synthesis of molecular nanostructures often requires the variation of several parameters, such as stoichiometry, pH, counter-ion etc. Here, the authors report a flow reaction array with algorithmic control which is used as a ‘search engine’ to isolate six nanoscale clusters from a massive parameter space.
- Hong-Ying Zang
- , Andreu Ruiz de la Oliva
- & Leroy Cronin
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Article |
Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage
Metallofullerenes typically have polar single bonds between metals and non-metals. Here, through arc-discharge experiments, the authors observe the formation of an endohedral fullerene with an encapsulated tri-coordinate μ3-carbon centre and a stable titanium-carbon double bond.
- A. L. Svitova
- , K. B. Ghiassi
- & A. A. Popov
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Article |
Improving the stability and optical properties of germanane via one-step covalent methyl-termination
Germanane is a two-dimensional material that represents a promising alternative to graphene for applications in electronics and optoelectronics. Here, Jiang and colleagues demonstrate that germanane’s optical properties can be improved by methyl-termination instead of hydrogen.
- Shishi Jiang
- , Sheneve Butler
- & Joshua E. Goldberger
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Article
| Open AccessExtracellular palladium-catalysed dealkylation of 5-fluoro-1-propargyl-uracil as a bioorthogonally activated prodrug approach
A bioorthogonal organometallic reaction is a biocompatible and chemospecific process. Here, the authors report the bioorthogonal generation of 5-fluorouracil from a biologically inert alkylated precursor by extracellular palladium catalysis, and assess its antiproliferative properties in vitro.
- Jason T. Weiss
- , John C. Dawson
- & Asier Unciti-Broceta
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Capsule-controlled selectivity of a rhodium hydroformylation catalyst
The selectivity and activity of enzymes is largely attributed to the well-defined cavities around their active sites, defined by the secondary coordination sphere. Here, the authors show that similar strategies may be applied to tune the selectivity of synthetic rhodium hydroformylation catalysts.
- Vladica Bocokić
- , Ayfer Kalkan
- & Joost N. H. Reek
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Hydrodefluorination of carbon–fluorine bonds by the synergistic action of a ruthenium–palladium catalyst
Selective hydrodefluoridization is important as an industrial reaction and in the disposal of chlorofluorocarbons. Here, the authors prepare a heterodimetallic ruthenium–palladium complex, which is active in the hydrodefluorination of aromatic and aliphatic molecules under mild reaction conditions.
- Sara Sabater
- , Jose A. Mata
- & Eduardo Peris
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Trinuclear zinc complexes for biologically relevant μ3-oxoanion binding and carbon dioxide fixation
Molecular models of the biologically relevant oxoanion-bridged trinuclear zinc cluster found in numerous enzymatic active sites are desirable. Cao et al. report the synthesis of a trinuclear zinc scaffold, pre-organized to capture oxoanions, and its ability to catalytically convert CO2to carbonates in solution.
- Xiao Liu
- , Pingwu Du
- & Rui Cao
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Probing the nature of gold–carbon bonding in gold–alkynyl complexes
Fundamental understanding of gold–carbon bonding in homogeneous catalysts is vital for improved catalyst design, although spectroscopic information is limited. Here, the authors probe the bonding in gold–alkyne complexes using a combination of photoelectron spectroscopy and ab initiocalculations.
- Hong-Tao Liu
- , Xiao-Gen Xiong
- & Lai-Sheng Wang
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Organic topological insulators in organometallic lattices
Topological insulators are bulk insulators with conductive boundary states, and until now have been based only on inorganic materials. Wang et al.use first-principles calculations to predict a class of organic topological insulators based on organometallic lattices exhibiting robust topological edge states.
- Z.F Wang
- , Zheng Liu
- & Feng Liu