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Article
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Isotope engineering achieved by local coordination design in Ti-Pd co-doped ZrCo-based alloys
Hydrogen isotope effect in metal-hydrogen systems disturbs precise Deuterium/Tritium (D/T) ratio control. Here, the authors demonstrate a local coordination strategy that comprises thermodynamic destabilization with vibration enhancement of interstitial isotopes for isotope engineering.
- Jiacheng Qi
- , Xu Huang
- & Lixin Chen
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Article
| Open Access
Reduction of Li+ within a borate anion
Chemical reduction of alkali cations to their metals is extremely challenging. Here, the authors synthesized a series of redox-active borate anions stabilized by bipyridine ligands which can reduce lithium ions generating elemental lithium metal and borate radicals.
- Haokun Li
- , Jiachen Yao
- & Zhenpin Lu
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Article
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Remote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins
The synthesis of highly substituted olefins has been pursued for decades. Here, the authors show a carbonyl-directed sequential Heck/isomerization/C–H arylation of alkenes for modular synthesis of stereodefined all-carbon tetrasubstituted olefins.
- Runze Luan
- , Ping Lin
- & Weiping Su
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Article
| Open Access
Rationally designed nanotrap structures for efficient separation of rare earth elements over a single step
Extracting rare earth elements (REEs) from wastewater is essential for the growth of an eco-friendly sustainable economy but separating individual rare earth elements remains challenging. Here, the authors report a REE nanotrap that features dense uncoordinated carboxyl groups and triazole N atoms in a two-fold interpenetrated metalorganic framework which is highly responsive to the size variation of rareearth ions.
- Qing-Hua Hu
- , An-Min Song
- & Jian-Ding Qiu
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Article
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Photooxidation driven formation of Fe-Au linked ferrocene-based single-molecule junctions
Metal-metal interfaces hold promise as contacting moieties for single-molecule devices with tunable functionality, yet the direct bonding has remained a challenge. Here, Lee et al. report the formation of Fe-Au bond without chemical ligand support in ferrocene-based molecular junctions.
- Woojung Lee
- , Liang Li
- & Latha Venkataraman
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Article
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Coordination-induced O-H/N-H bond weakening by a redox non-innocent, aluminum-containing radical
Coordination-induced bond weakening (CIBW) by redox-active metals is used to weaken bonds in water and ammonia to facilitate proton-coupled electron transfer but achieving CIBW using aluminium as abundant metal is challenging. Here, the authors report a system that uses aluminum with a redox non-innocent ligand to achieve CIBW of O-H and N-H bonds.
- Soumen Sinhababu
- , Roushan Prakash Singh
- & Neal P. Mankad
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Article
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A zero-valent palladium cluster-organic framework
Ultrasmall metallic clusters receive great attention for atom-efficient catalysts. Here a metallic cluster–organic framework is synthesized and characterized; authors demonstrate its stability and catalytic proficiency, paving the way for molecular-scale metal nanoparticle interlocking.
- Xiyue Liu
- , James N. McPherson
- & Kasper S. Pedersen
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Article
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Defect passivation in methylammonium/bromine free inverted perovskite solar cells using charge-modulated molecular bonding
Molecular passivation is promising for improving the performance and operation stability of perovskite solar cells. Here, authors employ piperazine dihydriodide to strengthen adhesion to MA-free perovskite via −NH2I and Mulliken charge distribution, realizing charge-regulated molecular passivation.
- Dhruba B. Khadka
- , Yasuhiro Shirai
- & Kenjiro Miyano
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Article
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Hydrogen bond unlocking-driven pore structure control for shifting multi-component gas separation function
C2H4 is one of the most important chemical raw materials. Here, the authors report that tuning of pore structure shifts the multi-component gas separation function, enabling one-step production of high-purity C2H4 in the quaternary mixture.
- Rong Yang
- , Yu Wang
- & Kai-Jie Chen
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Article
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Catalytic hydrogenation of olefins by a multifunctional molybdenum-sulfur complex
Exploration of molybdenum complexes as homogeneous hydrogenation catalysts has garnered significant attention, but hydrogenation of unactivated olefins under mild conditions are scarce. Here, the authors report the synthesis of a cationic Mo(II) complex, which exhibits intriguing reactivity toward C2H2 and H2 under ambient pressure.
- Minghui Xue
- , Zhiqiang Peng
- & Wenguang Wang
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Article
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Photocatalytic aerobic oxidation of C(sp3)-H bonds
The authors report a family of photocatalysts containing Ce active sites and perylene diimide ligands for the aerobic oxidation of substituted toluene, ethylbenzene, benzyl alcohol, thioanisole, and benzylamine in acetonitrile.
- Lei Zhang
- , Run-Han Li
- & Ya-Qian Lan
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Article
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Self-assembly of the smallest and tightest molecular trefoil knot
The synthesis of molecular knots remains challenging. Here, the authors report the synthesis of a chiral molecular trefoil metallaknot by self-assembly which contains only 54 atoms in the backbone.
- Zhiwen Li
- , Jingjing Zhang
- & Richard J. Puddephatt
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Article
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Atomic-resolution structure analysis inside an adaptable porous framework
Single crystal X-ray diffraction is one of the most powerful structure elucidation tools, but it’s challenging to determine complex structures. Here the authors report a metal-organic framework for encapsulation and immobilization of various guests using highly ordered internal water network, obtaining high quality atomic-resolution data.
- Yuki Wada
- , Pavel M. Usov
- & Masaki Kawano
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Article
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A hard molecular nanomagnet from confined paramagnetic 3d-4f spins inside a fullerene cage
Shortening the inter-spin distance is an effective way to enhance magnetic coupling. However, it is typically challenging to change the inter-ion distance in most magnetic systems. Here, Huang et al present a strategy for enhancing magnetic interactions, by confining a molecular magnetic system inside a carbon fullerene cage, leading to enhanced magnetic properties.
- Chenli Huang
- , Rong Sun
- & Song Gao
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Article
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Thermally-induced atropisomerism promotes metal-organic cage construction
While heat modification is ubiquitous in biologic systems, it remains a significant challenge in artificial systems. Here the authors demonstrate thermal regulation of conversion between different rigid macrocycle atropisomers and related self-assemblies.
- Jiaqi Liang
- , Shuai Lu
- & Han-Yuan Gong
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Article
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Selective synthesis of tightly- and loosely-twisted metallomacrocycle isomers towards precise control of helicity inversion motion
Molecular twist is a characteristic component of molecular machines. Here the authors report a kinetically selective synthesis of tightly- and loosely-twisted isomers of a trinuclear Pd-macrocycle and their markedly different molecular behaviours.
- Tomoki Nakajima
- , Shohei Tashiro
- & Mitsuhiko Shionoya
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Article
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Crown-hydroxylamines are pH-dependent chelating N,O-ligands with a potential for aerobic oxidation catalysis
Despite the rich coordination chemistry, hydroxylamines are rarely used as ligands for transition metal coordination compounds. Here the authors designed macrocyclic poly-N-hydroxylamines that form complexes containing a d-metal ion and coordinate by up to six hydroxylamine fragments.
- Vladislav K. Lesnikov
- , Ivan S. Golovanov
- & Alexey Yu. Sukhorukov
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Article
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A silylene-stabilized ditin(0) complex and its conversion to methylditin cation and distannavinylidene
Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Here, the authors report the synthesis of a silylene-stabilized ditin(0) complex by reduction of a silylene-supported dibromostannylene and its conversion to methylditin cation and distannavinylidene
- Shaozhi Du
- , Fanshu Cao
- & Zhenbo Mo
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Article
| Open Access
Fabrication of robust and cost-efficient Hoffmann-type MOF sensors for room temperature ammonia detection
Developing fast-responsive NH3 sensors at room temperature is challenging. Here the authors developed robust Hoffmann-type MOF based NH3 sensors with a low detection limit (25 ppb) and quick response (5 s). The sensors exhibit high NH3 selectivity, stability, and easy recovery.
- Sa Wang
- , Yu Fu
- & Zhenjie Zhang
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Article
| Open Access
Photocatalytic CO2 reduction to syngas using metallosalen covalent organic frameworks
Here, the authors report a gram-scale, one-step synthesis of metallosalen-covalent organic frameworks (M(salen)-COFs) without vacuum evacuation. M(salen)-COFs exhibit good crystallinity and adjustable activities in CO2 photoreduction to syngas.
- Wei Zhou
- , Xiao Wang
- & Wei-Qiao Deng
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Article
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Atomically precise ultrasmall copper cluster for room-temperature highly regioselective dehydrogenative coupling
Three-component dehydrogenative coupling reactions represent important and practical methodologies for forging new C–N bonds and C–C bonds but achieving all-in-one dehydrogenative coupling functionalization by a single catalytic system remains a great challenge. Here, the authors develop a rigid flexible-coupled copper using a tridentate N-heterocyclic carbene ligand to achieve dehydrogenative coupling using a single catalyst system.
- Teng Jia
- , Yi-Xin Li
- & Shuang-Quan Zang
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Article
| Open Access
Electroluminescence and hyperphosphorescence from stable blue Ir(III) carbene complexes with suppressed efficiency roll-off
Deep-blue emitters and corresponding light-emitting devices are still in the progress to meet industrial standards. Here, the authors report catalytic interconversion of isomeric iridium(III) complexes and achieve true-blue emission and operational half-lifetime of over 10,000 h for tandem devices.
- Jie Yan
- , Dong-Ying Zhou
- & Yun Chi
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Article
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Dynamic and transformable Cu12 cluster-based C-H···π-stacked porous supramolecular frameworks
The assembly of cluster-based π-stacked porous supramolecular frameworks presents daunting challenges. Here, the authors report a dynamic and transformable supramolecular framework based on Cu12 cluster and C-H···π-stacking with permanent porosity
- Chengkai Zhang
- , Zhi Wang
- & Di Sun
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Article
| Open Access
Hydrolase mimic via second coordination sphere engineering in metal-organic frameworks for environmental remediation
Enzymatic degradation of pollutants under mild conditions is promising for efficient degradation of environmental contaminants under facile operation conditions, but natural enzymes tend to lose enzymatic activity in environmental application scenarios. Here, the authors report a metal-organic frameworks-based artificial enzyme system to achieve high hydrolytic activity under mild conditions.
- Xin Yuan
- , Xiaoling Wu
- & Wenyong Lou
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Article
| Open Access
Synthesis of metalla-dual-azulenes with fluoride ion recognition properties
Azulene-based conjugated systems are of great interests due to their unusual structures and photophysical properties but incorporation of a transition metal into azulene skeleton presents remains elusive. Here, the authors describe an efficient [5 + 2] annulation reaction for the rapid construction of a metalla-dual-azulene.
- Hai-Cheng Liu
- , Kaidong Ruan
- & Haiping Xia
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Article
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Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
The introduction of metal sites into polyoxometalates is key for tuning their structure and reactivity but the complex mechanisms which govern metal functionalization of polyoxometalates are still poorly understood. Here, the authors report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di- metal-functionalization of a prototype molecular vanadium oxide cluster
- Stefan Repp
- , Moritz Remmers
- & Carsten Streb
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Article
| Open Access
Synthesis and characterization of a formal 21-electron cobaltocene derivative
The synthesis and isolation of d-block metallocenes with more than 18-electron is challenging since metal–carbon bonds become weaker with increasing deviation from the 18-electron configuration. Here the authors report a formal 21-electron cobaltocene derivative by coordination of a two-electron donor to a 19-electron cobaltocene derivative while maintaining the cobalt-carbon bonds.
- Satoshi Takebayashi
- , Jama Ariai
- & Kazunobu Sato
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Article
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A route to metalloligands consolidated silver nanoclusters by grafting thiacalix[4]arene onto polyoxovanadates
Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters (NCs), but their synthesis and subsequent installation onto metal NCs remains a significant challenge. Here, the authors demonstrate the synthesis of two atomically precise silver NCs by controlling reaction temperature and demonstrate thermal induced structure transformation between the clusters during a temperature-dependent assembly process.
- Zhi Wang
- , Yan-Jie Zhu
- & Di Sun
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Article
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Doubly N-confused and ring-contracted [24]hexaphyrin Pd-complexes as stable antiaromatic N-confused expanded porphyrins
In the chemistry of porphyrinoids, expanded porphyrins and N-confused porphyrins (NCP) are two important newcomers but antiaromatic expanded NCPs have not been isolated before. Here, the authors report the synthesis of doubly N-confused and ring-contracted hexaphyrin PdII complexes.
- Fuying Luo
- , Le Liu
- & Jianxin Song
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Article
| Open Access
Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Here, the authors report an on-cycle mechanism for CoCl2bpy2 catalyzed Negishi-type cross-coupling describing a full catalytic cycle for this reaction using multiple spectroscopic studies.
- Xu Luo
- , Dali Yang
- & Aiwen Lei
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Article
| Open Access
Unusual nuclear exchange within a germanium-containing aromatic ring that results in germanium atom transfer
Controlled atomic delivery is a desirable synthetic process. Here a germanium-substituted phenyl anion is shown to act as a germanium atom transfer reagent and demonstrated by the preparation of well-defined molecular germanium species.
- Ryohei Nishino
- , Norihiro Tokitoh
- & Yoshiyuki Mizuhata
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Article
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Location-selective immobilisation of single-atom catalysts on the surface or within the interior of ionic nanocrystals using coordination chemistry
The authors report the location-selective immobilisation of single Pt atoms on the surface or within the interior of CdSe nanoplatelets using coordination chemistry and show location-dependent photocatalytic reactivity.
- Kenichi Endo
- , Masaki Saruyama
- & Toshiharu Teranishi
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Article
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Carbene-stabilized enantiopure heterometallic clusters featuring EQE of 20.8% in circularly-polarized OLED
Chiral coinage metal clusters show promise for use in emerging circularly polarized light-emitting materials and diodes but research on efficient circularly polarized organic light-emitting diodes (CP-OLEDs) with enantiopure metal clusters remains elusive. Herein, the authors design a multidentate chiral N-heterocyclic carbene (NHC) ligand which is used in the synthesis of enantiopure Au(I)-Cu(I) clusters with exceptional stability and demonstrate application of these clusters in the fabrication of CP-OLEDs
- Xiao-Hong Ma
- , Jing Li
- & Shuang-Quan Zang
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Matters Arising
| Open Access
Reply to: On the existence of collective interactions reinforcing the metal-ligand bond in organometallic compounds
- Vojtech Šadek
- , Shahin Sowlati-Hashjin
- & Cina Foroutan-Nejad
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Article
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Isolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations
Tetrylones show unique electronic properties and display potantial as soluble molecular allotropes, but until now, the chemistry of Tetrylone homologs remains underexplored. Here, the authors describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis silylene ligand and explore their reactivity.
- Xuyang Wang
- , Binglin Lei
- & Zhenbo Mo
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Article
| Open Access
Architector for high-throughput cross-periodic table 3D complex building
Rare-earth and actinide complexes are critical for a wealth of clean-energy applications but Three dimensional (3D) structural generation and prediction for these organometallic systems remains challenging. Here, the authors propose a high-throughput in-silico synthesis code for s-, p-, d-, and f-block mononuclear organometallic complexes.
- Michael G. Taylor
- , Daniel J. Burrill
- & Ping Yang
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Article
| Open Access
A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl
Replicating the seminal reactions of transition metals with p-block species is often very challenging. Here, the authors present a step-for-step main-group replica of the historical Fischer carbene synthesis, providing bora-Fischer carbene species.
- Marcel Härterich
- , Alexander Matler
- & Holger Braunschweig
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Article
| Open Access
Direct synthesis of oxalic acid via oxidative CO coupling mediated by a dinuclear hydroxycarbonylcobalt(III) complex
Oxidative coupling of CO is a straightforward but currently underdeveloped economically benign synthetic route to target α-diketones. Here, the authors synthesize a rare coplanar dinuclear hydroxycarbonylcobalt(III) complex and demonstrate that the Co – carboxylate bonds can be easily cleaved leading to the formation of oxalic acid.
- Yingzhuang Xu
- , Songyi Li
- & Huayi Fang
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Article
| Open Access
Atomically precise gold nanoclusters at the molecular-to-metallic transition with intrinsic chirality from surface layers
Chiral metal nanoclusters prepared from achiral ligands generally contain chiral kernel structures. Here, the authors report an alternative type of gold nanoclusters whose intrinsic chirality arises solely from the arrangement of the organic components on their surface.
- Li-Juan Liu
- , Fahri Alkan
- & Jian He
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Article
| Open Access
Rational design of N-heterocyclic compound classes via regenerative cyclization of diamines
Introducing unknown compound classes is the key to extent the chemical space qualitatively. Here the authors report on a concept to design heterocyclic compound classes rationally and the synthesis of unknown classes of N-heterocyclic compounds
- Robin Fertig
- , Felix Leowsky-Künstler
- & Rhett Kempe
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Article
| Open Access
Engineering β-ketoamine covalent organic frameworks for photocatalytic overall water splitting
Covalent organic frameworks (COFs) are an emerging type of crystalline and porous photocatalysts for hydrogen evolution. Here, the authors report a β-ketoamine COF by systematically engineering N-sites, architecture, and morphology for improved water splitting activity.
- Yan Yang
- , Xiaoyu Chu
- & Ya-Qian Lan
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Article
| Open Access
Preferential molecular recognition of heterochiral guests within a cyclophane receptor
The design of synthetic supramolecular receptors capable of enantioselective molecular recognition is challenging. Here the authors report a perylene bisimide-based receptor that forms heterochiral host-guest complexes upon aromatic guests encapsulation; guest recognition can be modulated by peripheral substitution of the binding site.
- Manuel Weh
- , Kazutaka Shoyama
- & Frank Würthner
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Article
| Open Access
Selective and rapid extraction of trace amount of gold from complex liquids with silver(I)-organic frameworks
The development of adsorbents for extracting gold from solutions is desirable from an environmental and economical point of view. Here, the authors report two two-dimensional silver(I)‒organic frameworks that enable selective sensing and extraction of gold from aqueous solutions, including seawater and solutions of e-waste.
- Jie Luo
- , Xiao Luo
- & Dan Li
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Article
| Open Access
A one-dimensional conductive metal-organic framework with extended π-d conjugated nanoribbon layers
2D and 3D conductive MOFs have performed well in the fields of energy and catalysis. Here, authors synthesise a 1D conductive MOF in which DDA ligands are connected by double Cu ions, forming nanoribbon layers with π-d conjugated nanoribbon planes and out-of-plane π-π stacking, which facilitates charge transport along two dimensions.
- Shengcong Shang
- , Changsheng Du
- & Jianyi Chen
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Article
| Open Access
Data-driven design of molecular nanomagnets
Three decades of research in molecular nanomagnets have enabled the preparation of compounds displaying magnetic memory at liquid nitrogen temperature. Here, the authors provide an innovative framework for the design of molecular magnets based on data mining, and develop an interactive dashboard to visualize the dataset.
- Yan Duan
- , Lorena E. Rosaleny
- & Alejandro Gaita-Ariño
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Article
| Open Access
Plastic bending in a semiconducting coordination polymer crystal enabled by delamination
Coordination polymers are normally considered to be brittle due to the dominance of directional coordination bonding. Here the authors report the plastic bending in a semiconducting coordination polymer crystal enabled by delamination.
- Lian-Cai An
- , Xiang Li
- & Xian-He Bu
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Article
| Open Access
Direct synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand
Direct conversion of dinitrogen to organonitrogen compounds is a challenging goal in nitrogen fixation chemistry. Here, the authors report the catalytic formation of cyanate anion from dinitrogen under ambient conditions using a molybdenum complex.
- Takayuki Itabashi
- , Kazuya Arashiba
- & Yoshiaki Nishibayashi
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Article
| Open Access
Construction of conducting bimetallic organic metal chalcogenides via selective metal metathesis and oxidation transformation
Organic metal chalcogenides (OMCs) are organic-inorganic hybrid materials with continuous M-X (X = S, Se, Te) networks that are covalently connected by organic ligands. Here authors report a family of bimetallic OMCs synthesized via selective metal metathesis and oxidation transformation.
- Yigang Jin
- , Yuhui Fang
- & Wei Xu
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Article
| Open Access
Organic radicals stabilization above 300 °C in Eu-based coordination polymers for solar steam generation
Organic radicals have potential applications in a variety of fields, including energy conversion. Here, the authors report Eu-based coordination polymers that enable the stabilization of organic radicals up to 350 °C; these systems can be used to enhance solar steam generation.
- Xinhe Ye
- , Lai-Hon Chung
- & Jun He
Integrating spin-dependent emission and dielectric switching in FeII catenated metal-organic frameworks