Featured
-
-
Article
| Open AccessCovalent bond shortening and distortion induced by pressurization of thorium, uranium, and neptunium tetrakis aryloxides
The properties of actinide complexes depend on the ionic versus covalent nature of the bonds. Here, the authors report that pressure can distort actinide-oxygen bonding; differences seen for Th, U and Np result from the decreasing size of the atoms.
- Jacob J. Shephard
- , Victoria E. J. Berryman
- & Simon Parsons
-
Article
| Open AccessFrom an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl2(pyrazine)2 coordination solids
Achieving high conductivity in metal-organic solids can be challenging, due to the difficulty of obtaining a good overlap between the d-orbitals of the metal and the π-orbitals of the organic molecule. Here, the authors present two coordination solids, VCl2(pyrazine)2 and TiCl2(pyrazine)2, with remarkably different electrical conductivity. While the former is an insulator, the latter displays the highest conductivity of any octahedrally coordinated metal ions based metal-organic solid.
- Panagiota Perlepe
- , Itziar Oyarzabal
- & Rodolphe Clérac
-
Article
| Open AccessN-Heterocyclic carbene-based C-centered Au(I)-Ag(I) clusters with intense phosphorescence and organelle-selective translocation in cells
Photoluminescent gold clusters have unique chemical and physical properties based on their perturbed electronic structures. Here, the authors report the synthesis of carbon-centered Au(I)-Ag(I) clusters with high phosphorescence quantum yields using N-heterocyclic carbene ligands.
- Zhen Lei
- , Mizuki Endo
- & Mitsuhiko Shionoya
-
Article
| Open AccessLinking oxidative and reductive clusters to prepare crystalline porous catalysts for photocatalytic CO2 reduction with H2O
A crystalline hetero-metallic cluster catalyst based on a covalent organic framework strategy is reported. The catalyst can facilitate both photocatalytic oxidative and reductive reactions leading to efficient production of HCOOH from CO2 and H2O.
- Jie Zhou
- , Jie Li
- & Ya-Qian Lan
-
Article
| Open AccessMeasuring anion binding at biomembrane interfaces
Quantification of anion binding by molecular receptors within lipid bilayers is challenging. Here, the authors synthesise a high-affinity macrocyclic anion receptor which provides insights into determinants of anion binding within lipid bilayers.
- Xin Wu
- , Patrick Wang
- & Philip A. Gale
-
Article
| Open AccessSelective separation of light rare-earth elements by supramolecular encapsulation and precipitation
The separation of the rare-earth elements is a significant scientific challenge. Here, the authors report the selective precipitation of the light rare-earths as supramolecular capsules from acidic, industrially relevant, mixed-metal solutions.
- Joseph G. O’Connell-Danes
- , Bryne T. Ngwenya
- & Jason B. Love
-
Article
| Open AccessAmmonia for post-healing of formamidinium-based Perovskite films
Solvents used for perovskite film fabrication not only dissolve the precursors but also play a role in the crystallization process. Here, authors study the role of transamination reactions in the underlying degradation mechanism of formamidinium-containing perovskites in aliphatic amines environment.
- Zhipeng Li
- , Xiao Wang
- & Shuping Pang
-
Article
| Open AccessExploration of glassy state in Prussian blue analogues
Developments in Prussian blue analogues (PBAs) have centred solely on their crystalline state. Here, the authors describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties.
- Nattapol Ma
- , Ryo Ohtani
- & Satoshi Horike
-
Article
| Open AccessContrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules
The reasons for which many low-coordinate complexes exhibit bent geometry, rather than a higher symmetry, are still under debate. Here, the authors use high-pressure crystallography to examine whether low-coordinate f-block molecules become more planar or pyramidal under pressure; which happens is dictated by the dipole moment of the complex and the volume of the planar form.
- Amy N. Price
- , Victoria Berryman
- & Polly L. Arnold
-
Article
| Open AccessPreparation of photonic molecular trains via soft-crystal polymerization of lanthanide complexes
Soft-crystals are molecular solids with highly ordered structures. Here, authors report the soft-crystal copolymerization of green-luminescent Tb(III) and yellow-luminescent Dy(III) complexes, and study the long-range energy transfer from one crystal to the other.
- Pedro Paulo Ferreira da Rosa
- , Yuichi Kitagawa
- & Yasuchika Hasegawa
-
Article
| Open AccessPhotochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes
The synthesis and isolation of uranium(VI) nitride complexes remains challenging. Here, the authors report an example of transition metal (TM) stabilized U(VI) nitride complexes, generated via photolysis of azide-bridged U(IV)-TM precursors.
- Xiaoqing Xin
- , Iskander Douair
- & Congqing Zhu
-
Article
| Open AccessRu(II) photocages enable precise control over enzyme activity with red light
The cytochrome P450 enzyme CYP1B1 is overexpressed in a variety of tumors, and is correlated with poor treatment outcomes; thus, it is desirable to develop CYP1B1 inhibitors to restore chemotherapy efficacy. Here the authors describe the creation of light-triggered CYP1B1 inhibitors as “prodrugs”, and achieve >6000-fold improvement in potency upon activation with low-energy (660 nm) light.
- Dmytro Havrylyuk
- , Austin C. Hachey
- & Edith C. Glazer
-
Article
| Open AccessParamagnetic encoding of molecules
Molecules offer enormous capacity for information storage. Here, the authors show that information can be encoded into molecules with sequences of paramagnetic lanthanide ions, and decoded using nuclear magnetic resonance spectroscopy.
- Jan Kretschmer
- , Tomáš David
- & Miloslav Polasek
-
Article
| Open AccessTandem utilization of CO2 photoreduction products for the carbonylation of aryl iodides
A Ni-based MOF catalyst is reported to facilitate the photocatalytic reduction of CO2 to CO, a low-value product. In tandem, the as-produced CO is used as a reactant in the Pd-catalyzed carbonylation of aryl halides and other fine organic chemicals.
- Yuan-Sheng Xia
- , Meizhong Tang
- & Ya-Qian Lan
-
Article
| Open AccessCoordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity
Coordination environments around metal sites are important in electrocatalysis. Here, Ni metalloid oxidation produces oxyanion doped amorphous Ni-oxyhydroxides where substitution with phosphorus is found to boost methanol electrooxidation activity.
- Shanlin Li
- , Ruguang Ma
- & Jiacheng Wang
-
Article
| Open AccessAchieving large thermal hysteresis in an anthracene-based manganese(II) complex via photo-induced electron transfer
Achieving magnetic bistability with large thermal hysteresis is still a challenge in material science. Here, the authors report a Mn(II) chain complex that enables light-induced magnetic bistability with a 177 K thermal hysteresis loop.
- Ji-Xiang Hu
- , Qi Li
- & Guo-Ming Wang
-
Article
| Open AccessOutpacing conventional nicotinamide hydrogenation catalysis by a strongly communicating heterodinuclear photocatalyst
Although multinuclear, supramolecular photocatalysts show promise in their ability to separate the processes required for lightdriven energy production into light absorption, charge separation and fuel production by individual parts of the molecule, mechanistic understanding of the performance limiting processes are lacking. Here the authors synthesize two new dinuclear catalysts and compare them to a benchmark through detailed spectroscopic studies, obtaining significant chemical insight.
- Linda Zedler
- , Pascal Wintergerst
- & Sven Rau
-
Article
| Open AccessSymmetry collapse due to the presence of multiple local aromaticity in Ge244−
Gaining insight on the structural transformations from atomic clusters to bulk materials is challenging. Here the authors synthesize a continuous cluster of germanium Ge244−, which can be viewed as two terminal Ge9 units bridged via a Ge6 central fragment, and characterize it by several techniques including X-ray diffraction; theoretical analysis indicates the presence of three aligned independent aromatic fragments.
- Hong-Lei Xu
- , Nikolay V. Tkachenko
- & Zhong-Ming Sun
-
Article
| Open AccessStructural transformation and catalytic hydrogenation activity of amidinate-protected copper hydride clusters
Copper hydrides have been studied for their exciting structural chemistry and applications in hydrogenation catalysis. Here, the authors uncover the role of the amidinate ligand in yielding two closely related copper hydride clusters with quite different catalytic hydrogenation activity.
- Chun-Yu Liu
- , Shang-Fu Yuan
- & Quan-Ming Wang
-
Article
| Open AccessCollective interactions among organometallics are exotic bonds hidden on lab shelves
The authors introduce a novel type of chemical bond termed collective bond, which is based on long-range interactions between atoms not considered to be bonded within the Lewis formalisms. Collective bonding occurs among a large family of widely used organometallics.
- Shahin Sowlati-Hashjin
- , Vojtěch Šadek
- & Cina Foroutan-Nejad
-
Article
| Open AccessAn intermetallic molecular nanomagnet with the lanthanide coordinated only by transition metals
Molecular nanomagnets exhibit magnetic memory effect originating from each individual molecule. Here, the authors report an intermetallic nanomagnet based on a single ErIII center coordinated solely by three transition metals in a trigonal planar fashion.
- Michał Magott
- , Maria Brzozowska
- & Dawid Pinkowicz
-
Article
| Open AccessStructure and reactivity of germylene-bridged digold complexes
The number of metal complexes featuring gold-germanium bonds is limited. Here the authors report the preparation of germylene-bridged digold complexes complexes and study their structure, bonding, and reactivity.
- Liliang Wang
- , Guorong Zhen
- & Zhifang Li
-
Article
| Open AccessNuclearity enlargement from [PW9O34@Ag51] to [(PW9O34)2@Ag72] and 2D and 3D network formation driven by bipyridines
Controlling the structural transformations of metal clusters is challenging. Here, the authors synthesize a silver nanocluster and study the structural changes that take place upon reaction with bipyridine derivatives.
- Zhi Wang
- , Yan-Jie Zhu
- & Di Sun
-
Article
| Open AccessHyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics
Self-assembling nanostructures that trap guest molecules find applications in materials research and the life sciences. Here, authors describe how ultra-sensitive NMR reveals sub-types with broken symmetry that significantly impacts guest exchange.
- Jabadurai Jayapaul
- , Sanna Komulainen
- & Leif Schröder
-
Article
| Open AccessGeneration of a μ-1,2-hydroperoxo FeIIIFeIII and a μ-1,2-peroxo FeIVFeIII Complex
Iron coordination complexes can be used to gain insight on biologically relevant iron-oxygen compounds generated in iron metalloenzymes. Here, the authors characterise a μ-1,2-hydroperoxo FeIIIFeIII and a μ-1,2-peroxo FeIVFeIII, and study their reactivity in C-H activation.
- Stephan Walleck
- , Thomas Philipp Zimmermann
- & Thorsten Glaser
-
Article
| Open AccessIn situ-formed tetrahedrally coordinated double-helical metal complexes for improved coordination-activated n-doping
N-doping technologies are essential for high performance organic optoelectronics. Here, the authors report metalinkage diphenanthrolinetype ligands, which enable the formation of tetrahedrally coordinated double-helical metal complexes for coordination-activated n-doping.
- Ziyang Liu
- , Xiao Li
- & Lian Duan
-
Article
| Open AccessMacro- and atomic-scale observations of a one-dimensional heterojunction in a nickel and palladium nanowire complex
Low-dimensional heterojunctions are interesting for fundamental studies and applications, but their demonstrations have been limited to planar structures. Here the authors report synthesis and macro- and atomic scale characterization of a one-dimensional heterojunction formed by halogen-bridged metal-organic nanowires.
- Masanori Wakizaka
- , Shohei Kumagai
- & Shinya Takaishi
-
Article
| Open AccessSmall symmetry-breaking triggering large chiroptical responses of Ag70 nanoclusters
Having control over the chirality of metal nanoclusters is challenging. Here, the authors report the deracemization of silver nanoclusters and monitor the chiroptical responses.
- Xi-Ming Luo
- , Chun-Hua Gong
- & Thomas C. W. Mak
-
Article
| Open AccessHeterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet
Conductive and magnetically frustrated solids may enable the development of high-performance molecule-based spintronic devices. Here the authors report a conductive and magnetically frustrated metal–fullerene-bonded framework prepared from a redox-active dinuclear copper complex and lithium ion-encapsulated fullerenes.
- Yongbing Shen
- , Mengxing Cui
- & Masahiro Yamashita
-
Article
| Open AccessCyclopentadienyl coordination induces unexpected ionic Am−N bonding in an americium bipyridyl complex
The coordination environment has a great impact on the electronic structure, bonding and properties of metal complexes. Here the authors report a dinuclear organometallic americium complex that displays unexpectedly ionic Am−N bonding, but enhanced covalency in the Am−C bonds compared to its neodymium analogue.
- Brian N. Long
- , María J. Beltrán-Leiva
- & Thomas E. Albrecht-Schönzart
-
Article
| Open AccessGiant single-crystal-to-single-crystal transformations associated with chiral interconversion induced by elimination of chelating ligands
Crystalline materials that undergo large structural changes in response to external stimuli remain rare. Here the authors report a Zinc(II) complex that undergoes a two-step reversible single-crystal-to-single-crystal transformation via thermal removal of ethylene glycol chelating ligands; this results in large volume changes.
- Yun Li
- , Bo Zhao
- & Jun Tao
-
Article
| Open AccessCoordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4
Crystalline porous catalysts with single Cu sites are dedicated to exploring the dependence of CO2 electroreduction selectivity on the coordination environment of catalytic sites. The conductive MOF Cu-DBC with oxygen-coordinated Cu sites shows a high Faradaic efficiency ~80% of CO2-to-CH4.
- Yu Zhang
- , Long-Zhang Dong
- & Ya-Qian Lan
-
Article
| Open AccessExceptional uranium(VI)-nitride triple bond covalency from 15N nuclear magnetic resonance spectroscopy and quantum chemical analysis
Determining the covalency of actinide chemical bonding is a fundamentally important challenge. Here, the authors report a 15N nuclear magnetic resonance spectroscopy study of a terminal uranium-nitride, revealing exceptional NMR properties and covalency that redefine 15N NMR parameter space and actinide chemical bonding.
- Jingzhen Du
- , John A. Seed
- & Stephen T. Liddle
-
Article
| Open AccessA host–guest semibiological photosynthesis system coupling artificial and natural enzymes for solar alcohol splitting
Abiotic–biotic hybrid systems are promising to trap light for fuel and chemical transformation with high efficacy and selectivity. This study reports a coenzyme-mediated supramolecular host-guest semibiological system combining supramolecular catalyst and enzymes for solar alcohol splitting.
- Junkai Cai
- , Liang Zhao
- & Chunying Duan
-
Article
| Open AccessAccess to cationic polyhedral carboranes via dynamic cage surgery with N-heterocyclic carbenes
In comparison to their neutral or anionic counterparts, examples of cationic boron clusters remain scarce. Here, the authors prepare a variety of cationic polyhedral boranes by reacting closo-10-vertex carboranes with N-heterocyclic carbenes; the resulting open-cage cationic nido- arachno- or closo- derivatives are water soluble, which may enable unprecedented applications.
- Jan Vrána
- , Josef Holub
- & Aleš Růžička
-
Article
| Open AccessRevealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level
The preparation of chiral monolayer-protected metal clusters is interesting for their potential applications in a variety of fields, including catalysis. Here, the authors synthesize chiral Ag14 nanoclusters in an all-achiral environment, and decipher the origin of chirality at the molecular level; the solvent choice is key to achieve homochiral crystallization.
- Xiao-Qian Liang
- , Ying-Zhou Li
- & Di Sun
-
Article
| Open AccessManipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals
Pyroelectric materials exhibiting large and nearly constant pyroelectric coefficients over a wide temperature range are highly desirable. Here, the authors develop molecular [FeCo] crystals with continuous pyroelectricity, originating from a transition between three distinct electronic structures.
- Pritam Sadhukhan
- , Shu-Qi Wu
- & Osamu Sato
-
Article
| Open AccessEvidence for ligand- and solvent-induced disproportionation of uranium(IV)
Disproportion of uranium(IV) is rare, as it is usually the stable product of uranium(III) or (V) disproportionation. Here, the authors report uranium(IV) disproportionation to uranium(III) and (V) revealing ligand and solvent control over a key thermodynamic property of uranium
- Jingzhen Du
- , Iskander Douair
- & Stephen T. Liddle
-
Article
| Open AccessA chalcogenide-cluster-based semiconducting nanotube array with oriented photoconductive behavior
Interesting properties of carbon nanotubes prompt a search for diverse inorganic nanotubes. Here, the authors report a supertetrahedral chalcogenide cluster-based semiconducting nanotube array that exhibits high electric conductivity and oriented photoconductive behavior.
- Jiaqi Tang
- , Xiang Wang
- & Tao Wu
-
Article
| Open AccessRapid electron transfer via dynamic coordinative interaction boosts quantum efficiency for photocatalytic CO2 reduction
Positioning photosensitizer and catalyst complexes in photocatalytic systems is a promising method to direct desired electron transfers. Here, authors employ a dynamic coordinative interaction between molecular components to improve CO2 photoreduction to CO with a high quantum efficiency of 27.9%.
- Jia-Wei Wang
- , Long Jiang
- & Gangfeng Ouyang
-
Article
| Open AccessUnderstanding disorder and linker deficiency in porphyrinic zirconium-based metal–organic frameworks by resolving the Zr8O6 cluster conundrum in PCN-221
Zirconium-based metal–organic frameworks have defective structures that are useful in catalysis and gas storage. Here, the authors study the interplay between cluster disorder and linker vacancies in PCN-221 and propose a new structure model with tilted Zr6O4(OH)4 clusters rather than Zr8O6 clusters.
- Charlotte Koschnick
- , Robert Stäglich
- & Bettina V. Lotsch
-
Article
| Open AccessReversible formation of coordination bonds in Sn-based metal-organic frameworks for high-performance lithium storage
Tin-based alloying materials have been widely developed for lithium storage, but are limited by large volume variation. Herein, the authors created a new strategy of applying coordination chemistry to construct tin-based metal-organic frameworks which exhibited high-performance lithium storage property.
- Jingwei Liu
- , Daixi Xie
- & Peng Cheng
-
Article
| Open AccessVisible colorimetric dosimetry of UV and ionizing radiations by a dual-module photochromic nanocluster
Radiation dosimeters that measure ionizing radiations over a broad range and allow for direct readout are desirable. Here, the authors present a dual-mode photochromic thorium-based metal-organic nanocluster that enables direct visible colorimetric dosimetry of UV, β-ray, and γ-ray radiation.
- Huangjie Lu
- , Jian Xie
- & Jian Lin
-
Article
| Open AccessWater-oriented magnetic anisotropy transition
Little is known about how the orientation of coordinated water molecules affects the magnetic properties of single molecule magnets. Here the authors combine experimental data and theoretical calculations to study how the rotation of water molecules alters the magnetic anisotropy of a pyrazine-based cobalt(II) complex.
- Sheng-Qun Su
- , Shu-Qi Wu
- & Osamu Sato
-
Article
| Open AccessOn-surface preparation of coordinated lanthanide-transition-metal clusters
The preparation of lanthanide-transition metal clusters containing multiple lanthanide atoms remains challenging. Here, the authors present the controlled on-surface formation of ligand-stabilized heterometallic Ce/Au clusters containing two, three and four Ce atoms bridged by Au adatoms.
- Jing Liu
- , Jie Li
- & Yongfeng Wang
-
Article
| Open AccessA tris-spiro metalla-aromatic system featuring Craig-Möbius aromaticity
Spiroaromatic compounds are advantageous platforms for designing expanded aromatic systems. Herein, the authors present a tris‐spiro metalla‐aromatic Vanadium compound which forms a 40π Craig‐Möbius aromatic system.
- Zhe Huang
- , Yongliang Zhang
- & Zhenfeng Xi
-
Article
| Open AccessFacile electron delivery from graphene template to ultrathin metal-organic layers for boosting CO2 photoreduction
While solar-to-fuel energy conversion is appealing, materials require accessible active sites for reactants and rapid electron transfer steps. Here, authors support ultrathin metal-organic layers with graphene oxide as both template and electron mediator to boost CO2 photoreduction performance.
- Jia-Wei Wang
- , Li-Zhen Qiao
- & Tong-Bu Lu
-
Article
| Open AccessPhosphorus(III)-assisted regioselective C–H silylation of heteroarenes
Indole C-H silylation preferentially occurs at the C3 and C2 positions, while functionalization of the benzene core (C4-C7 sites) remains challenging. Here, the authors report a regioselective C7-H silylation of indole derivatives assisted by strong coordination of the palladium catalyst with a phosphorus directing group.
- Dingyi Wang
- , Xiangyang Chen
- & Zhuangzhi Shi
-
Article
| Open AccessCrossover between the adiabatic and nonadiabatic electron transfer limits in the Landau-Zener model
The Landau-Zener formula is a semiclassical model describing nonadiabatic transitions, but its range of validity in approaching the adiabatic regime had not been verified. The authors investigate electron transfer reactions in a series of mixed-valence complexes spanning the nonadiabatic throughout the adiabatic limit, and show that the model is valid in a broader range of conditions than previously expected.
- Guang Yuan Zhu
- , Yi Qin
- & Chun Y. Liu