Organometallic chemistry articles within Nature Communications

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  • Article
    | Open Access

    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

  • Article
    | Open Access

    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

  • Article
    | Open Access

    The development of a nitrogen fixation process that relies on the renewable energy, such as visible light, is an important goal in sustainable chemistry. Here, authors establish an iridium and molybdenum-catalysed ammonia formation from dinitrogen driven by visible light under ambient reaction conditions.

    • Yuya Ashida
    • , Yuto Onozuka
    •  & Yoshiaki Nishibayashi

  • Article
    | Open Access

    The stabilization of low-coordinate boron radicals is challenging, as they tend to form strong chemical bonds. Here the authors report the isolation and structural characterization of a dicoordinate boron radical featuring a π-donating amino and a π-accepting carbene ligand.

    • Yu-Jiang Lin
    • , Wei-Chun Liu
    •  & Ching-Wen Chiu

  • Article
    | Open Access

    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 Access

    Several strategies have been developed in recent years for therapeutic induction of ferroptosis in cancer. Here the authors report the design of two hypercarbon-centered gold(I) cluster prodrugs that induce ferroptosis of cancer cells, showing anti-tumor activity in preclinical bladder cancer models.

    • Kui Xiao
    • , Niyuan Zhang
    •  & Liang Zhao

  • Article
    | Open Access

    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 Access

    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 Access

    Elemental iron turns alkaline-earth metal complexes into highly active catalysts for the hydrogenation of alkenes, alkynes, imines and arenes. The proposed mechanism combines homogeneous catalysis by a soluble main group metal hydride complex with heterogeneous catalysis at the iron surface.

    • Christian Färber
    • , Philipp Stegner
    •  & Sjoerd Harder

  • Article
    | Open Access

    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 Access

    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 Access

    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 Access

    Mechanistic knowledge of photocatalytic nickel reactions is lacking, particularly with regards to the identities and oxidation states of key intermediates. Here the authors report a class of tridentate ligands that enables in-depth study of a representative cross-coupling reaction, wherein evidence for multiple intermediates in a Ni(I/III) cycle is presented.

    • Hanah Na
    •  & Liviu M. Mirica

  • Article
    | Open Access

    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 Access

    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 Access

    Photoresponsive compounds have potential applications in various fields, including the development of smart materials and switches. Here the authors report a gold(I) complex that undergoes multiple photoinduced color changes upon excitation of light at specific wavelengths, offering an enhanced storage capacity towards optical memory devices.

    • Nathan Man-Wai Wu
    • , Maggie Ng
    •  & Vivian Wing-Wah Yam

  • Article
    | Open Access

    Hydrogen-bonded inorganic frameworks are porous structures that may lead to novel materials with unprecedented properties and functionalities. Here the authors report the solid-state structures of orthosilicic acid-based hydrogen-bonded inorganic frameworks that can encapsulate small unsaturated cyclic molecules such as benzene, which are found stacked in parallel.

    • Masayasu Igarashi
    • , Takeshi Nozawa
    •  & Kazuhiko Sato

  • Article
    | Open Access

    Asymmetrically substituted phosphine ligands play a decisive role in catalysis, but their synthesis is rather challenging and often involves hazardous chemicals such as PCl3 or PH3. Here, the authors report the one-pot preparation of asymmetric phosphines from white phosphorus via a pentaphosphaferrocene based modular system, in which the transition metal complex can be reused.

    • Stephan Reichl
    • , Eric Mädl
    •  & Manfred Scheer

  • Article
    | Open Access

    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 Access

    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 Access

    Ternary heterometallic clusters often display intriguing structures and bonding. Here the authors prepare four [Sn2Sb5]3−-based clusters stabilized by coordination of a transition metal ion; analysis of their electronic structure reveals that the resulting cluster displays globally aromatic or antiaromatic character depending on the transition metal ion.

    • Yu-He Xu
    • , Nikolay V. Tkachenko
    •  & Zhong-Ming Sun

  • Article
    | Open Access

    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 Access

    Geometric E to Z double C=C bond isomerization is challenging as it requires kinetic trapping of the Z-isomer with injection of chemical energy. Here, the authors report a dinuclear Pd(I)−Pd(I) complex that mediates selective isomerization of E-1,3-dienes to the Z-isomers without photoirradiation.

    • Eiji Kudo
    • , Kota Sasaki
    •  & Tetsuro Murahashi

  • Article
    | Open Access

    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 Access

    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

  • Article
    | Open Access

    Artificial enzymes with reprogrammed and augmented catalytic activity and substrate selectivity have emerged to tackle limitations of noble metals or transition metal oxides. Here, the authors report Au25 clusterzymes which are endowed with high catalytic activity and selectivity in a range of enzyme-mimicking reactions.

    • Haile Liu
    • , Yonghui Li
    •  & Xiao-Dong Zhang

  • Article
    | Open Access

    Manganese-based hydrogenation catalysts are sensitive to high temperatures and may degrade under industrially relevant conditions. Here, the authors report a highly efficient manganese pincer pre-catalyst displaying high TOF values (up to 41 000 h−1) and stability (TON up to 200 000) at loadings as low as 5-200 ppm.

    • Wenjun Yang
    • , Ivan Yu. Chernyshov
    •  & Evgeny A. Pidko

  • Article
    | Open Access

    The reactivity of expanded porphyrins is highly influenced by their scaffold architecture. Here, the authors construct two nonaromatic dumbbell-shaped benzene- and pyridine-incorporating octaphyrins via Suzuki-Miyaura cross-coupling; depending on the framework, different coordination modes are obtained upon metallation with Pd(II).

    • Le Liu
    • , Zhiwen Hu
    •  & Jianxin Song

  • Article
    | Open Access

    The synthesis of closo-carboranes with more than 14 vertexes is challenging, and no examples have been reported to date. Herein, the authors present the long-sought 15- and 16-vertex closo-carboranes, in which the introduction of silyl groups to the two cage carbons is crucial; this finding might enable the synthesis of even larger carborane analogs in the future.

    • Fangrui Zheng
    • , Tsz Hin Yui
    •  & Zuowei Xie

  • Article
    | Open Access

    Examples of π single bonds in diradicals are rare, as they are typically unstable. Here, the authors describe a room temperature-stable closed-shell bicyclic tetrasilane that features a Si-Si π single bond between two of the non-adjacent Si centers.

    • Soichiro Kyushin
    • , Yoshikuni Kurosaki
    •  & Hideyuki Matsumoto

  • Article
    | Open Access

    The polyhedral skeletal electron pair theory (PESPT), also known as Wade-Mingos’ rules, defines a relationship between skeletal bonding electron pairs and structure of clusters. Here the authors report the synthesis, structure and computational studies of planar C2B4R4 carboranes that do not adhere to PESPT.

    • Wei Lu
    • , Dinh Cao Huan Do
    •  & Rei Kinjo

  • Article
    | Open Access

    Amides are versatile synthetic building blocks, however the general stability of the amide bond makes its selective transformation challenging. Here, the authors report a chemodivergent transformation of primary, secondary and tertiary amides by using 1,1-diborylalkanes as pro-nucleophiles.

    • Wei Sun
    • , Lu Wang
    •  & Chao Liu

  • Article
    | Open Access

    Catalytic asymmetric hydrosilylation of internal alkenes has proven elusive due to more favourable double bond reduction or isomerization. Here, the authors show an enantioselective Si-C coupling by hydrosilylation of activated alkenes using a palladium/phosphoramidite catalyst affording axially chiral succinimides.

    • Xing-Wei Gu
    • , Yu-Li Sun
    •  & Li-Wen Xu

  • Article
    | Open Access

    The controllable synthesis of organometallic polymers that can be used in ultrahigh information storage and anti-counterfeiting security has been an unsolved challenge. Here, the authors show sequence-controlled electrosynthesis of organometallic polymers with exquisite insertion of multiple and distinct monomers.

    • Jian Zhang
    • , Jinxin Wang
    •  & Mao Li

  • Article
    | Open Access

    Chiral 1,4-dienes are versatile building blocks in asymmetric synthesis, therefore their production is highly sought after. Here, the authors report an efficient enantioselective cross-hydroalkenylation of cyclic 1,3-dienes and terminal olefins affording chiral 1,4-dienes by using a chiral NHC-Ni(allyl)]BArF catalyst.

    • Yang Chen
    • , Liang Dang
    •  & Chun-Yu Ho

  • Article
    | Open Access

    Realizing efficient blue-emitting organic light-emitting diodes (OLEDs) with long operational lifetime is key to the development of future display technologies. Here, the authors report efficient host-guest and host-free OLEDs featuring designed carbene-metal-amide-type deep-blue photoemitters.

    • Patrick J. Conaghan
    • , Campbell S. B. Matthews
    •  & Alexander S. Romanov

  • Article
    | Open Access

    Metal-ligand δ and φ interactions, though considered weak, may be necessary for fully describing the electronic and geometric structures of certain compounds. Here, in actinide metallacycles, the authors discover two new types of M-L δ and φ back-bonds that contribute substantially to their unusual chemical behavior.

    • Morgan P. Kelley
    • , Ivan A. Popov
    •  & Ping Yang

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