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Inorganic and Physical Chemistry

  • Nature Communications | Article | open

    Carbonyl complexes have been studied extensively thanks to their rich substitution and redox chemistry, but most homoleptic transition metal carbonyl complexes isolated in the condensed phase are neutral or anionic. Here, the authors isolate two homoleptic carbonyl radical cations in the condensed phase; both 17-electron [Cr(CO)6]•+ salts.

    • Jan Bohnenberger
    • , Wolfram Feuerstein
    • , Daniel Himmel
    • , Michael Daub
    • , Frank Breher
    •  &  Ingo Krossing
  • Nature Communications | Article | open

    FeV(O)(OH) species have long been thought to play a role in a range of enzymatic oxidations, but their characterization has remained elusive. Here, using gas-phase ion spectroscopy, the authors characterize an FeV(O)(OH) species and find that its reactivity mimics that of Rieske oxygenases.

    • Margarida Borrell
    • , Erik Andris
    • , Rafael Navrátil
    • , Jana Roithová
    •  &  Miquel Costas
  • Nature Communications | Article | open

    In actinide chemistry, a longstanding bonding model describes metal-ligand binding using 6d-orbitals, with the 5f-orbitals remaining non-bonding. Here the authors explore the inverse-trans-influence — a case where the model breaks down — finding that the f-orbitals play a crucial role in dictating a trans-ligand-directed geometry.

    • Erli Lu
    • , Saira Sajjad
    • , Victoria E. J. Berryman
    • , Ashley J. Wooles
    • , Nikolas Kaltsoyannis
    •  &  Stephen T. Liddle
  • Nature Communications | Article | open

    Dilanthanide complexes that possess radical bridges exhibit enhanced magnetic exchange coupling, affording molecular magnets with high blocking temperatures. Here, the authors explore a series of dilanthanide-encapsulated fullerenes where the radical bridge is taken to its limit and the role is played by a single unpaired electron.

    • Fupin Liu
    • , Georgios Velkos
    • , Denis S. Krylov
    • , Lukas Spree
    • , Michal Zalibera
    • , Rajyavardhan Ray
    • , Nataliya A. Samoylova
    • , Chia-Hsiang Chen
    • , Marco Rosenkranz
    • , Sandra Schiemenz
    • , Frank Ziegs
    • , Konstantin Nenkov
    • , Aram Kostanyan
    • , Thomas Greber
    • , Anja U. B. Wolter
    • , Manuel Richter
    • , Bernd Büchner
    • , Stanislav M. Avdoshenko
    •  &  Alexey A. Popov
  • Nature Communications | Article | open

    Understanding the structural dynamics of flexible metal-organic frameworks at a thin-film level is key if they are to be implemented in devices. Here, Fischer and colleagues anchor flexible MOF crystallites onto substrates and identify a structural responsiveness that is distinct to that of the bulk.

    • Suttipong Wannapaiboon
    • , Andreas Schneemann
    • , Inke Hante
    • , Min Tu
    • , Konstantin Epp
    • , Anna Lisa Semrau
    • , Christian Sternemann
    • , Michael Paulus
    • , Samuel J. Baxter
    • , Gregor Kieslich
    •  &  Roland A. Fischer
  • Nature Communications | Article | open

    Gas-sensing materials are of increasing societal importance, but the ability to differentiate between similarly sized gases remains highly challenging. Here the authors report on a porous ferrimagnet that distinguishes diamagnetic N2 and CO2 gases from paramagnetic O2 gas.

    • Wataru Kosaka
    • , Zhaoyuan Liu
    • , Jun Zhang
    • , Yohei Sato
    • , Akihiro Hori
    • , Ryotaro Matsuda
    • , Susumu Kitagawa
    •  &  Hitoshi Miyasaka
  • Nature Communications | Article | open

    Halogen bonding can be exploited for the design of functional supramolecular materials, but heavier elements that are known to accept a halogen bond remain limited. Here, the authors demonstrate the formation of two-component cocrystals based on halogen bonds with phosphorus, arsenic and antimony.

    • Katarina Lisac
    • , Filip Topić
    • , Mihails Arhangelskis
    • , Sara Cepić
    • , Patrick A. Julien
    • , Christopher W. Nickels
    • , Andrew J. Morris
    • , Tomislav Friščić
    •  &  Dominik Cinčić
  • Nature Communications | Article | open

    Metal-organic frameworks are promising materials for proton exchange membrane fuel cells, but cumbersome ligand preparation and use of toxic metals or solvents hinders their application. Here, the authors report the green synthesis of a zirconium, amino acid-based MOF that displays high proton conductivity and excellent stability.

    • Sujing Wang
    • , Mohammad Wahiduzzaman
    • , Louisa Davis
    • , Antoine Tissot
    • , William Shepard
    • , Jérôme Marrot
    • , Charlotte Martineau-Corcos
    • , Djemel Hamdane
    • , Guillaume Maurin
    • , Sabine Devautour-Vinot
    •  &  Christian Serre
  • Nature Communications | Article | open

    While chemical bonding between carbon and the d- and p-block elements is relatively well-studied, that between carbon and the f-block elements remains comparatively poorly understood. Here, the authors synthesize a series of uranium−carbone complexes in which carbon forms an unprecedented double dative bond to uranium.

    • Wei Su
    • , Sudip Pan
    • , Xiong Sun
    • , Shuao Wang
    • , Lili Zhao
    • , Gernot Frenking
    •  &  Congqing Zhu
  • Nature Communications | Article | open

    Metal–organic framework glasses have emerged as a new family of melt-quenched glass, but have yet to display the accessible porosity of their crystalline counterparts. Here, Bennett and colleagues report that glasses derived from ZIF-76 parent materials possess 4 – 8 Å pores and exhibit reversible gas adsorption.

    • Chao Zhou
    • , Louis Longley
    • , Andraž Krajnc
    • , Glen J. Smales
    • , Ang Qiao
    • , Ilknur Erucar
    • , Cara M. Doherty
    • , Aaron W. Thornton
    • , Anita J. Hill
    • , Christopher W. Ashling
    • , Omid T. Qazvini
    • , Seok J. Lee
    • , Philip A. Chater
    • , Nicholas J. Terrill
    • , Andrew J. Smith
    • , Yuanzheng Yue
    • , Gregor Mali
    • , David A. Keen
    • , Shane G. Telfer
    •  &  Thomas D. Bennett
  • Nature Communications | Article | open

    The large-scale production of CS2 presents both environmental and biological hazards, yet adsorbents capable of CS2 capture remain scarcely explored. Here, Long and colleagues demonstrate that CS2 is adsorbed in diamine-appended metal–organic frameworks through a cooperative and chemically specific insertion process.

    • C. Michael McGuirk
    • , Rebecca L. Siegelman
    • , Walter S. Drisdell
    • , Tomče Runčevski
    • , Phillip J. Milner
    • , Julia Oktawiec
    • , Liwen F. Wan
    • , Gregory M. Su
    • , Henry Z. H. Jiang
    • , Douglas A. Reed
    • , Miguel I. Gonzalez
    • , David Prendergast
    •  &  Jeffrey R. Long
  • Nature Communications | Article | open

    Controlled switching of the spin state of transition metal ions is key in many enzymatic reactions, but difficult to replicate in synthetic systems. Here the authors report on an iron(III) porphyrin with a photochromic axial ligand that, in solution, reversibly switches between low-spin and high-spin upon irradiation with two different wavelengths.

    • Sreejith Shankar
    • , Morten Peters
    • , Kim Steinborn
    • , Bahne Krahwinkel
    • , Frank D. Sönnichsen
    • , Dirk Grote
    • , Wolfram Sander
    • , Thomas Lohmiller
    • , Olaf Rüdiger
    •  &  Rainer Herges
  • Nature Communications | Article | open

    Achieving control over the thermomechanical properties of functional materials is desirable, yet remains highly challenging. Here, the authors demonstrate continuous negative-to-positive tuning of thermal expansion in two Prussian blue analogues, by varying the concentration of adsorbed CO2.

    • Josie E. Auckett
    • , Arnold A. Barkhordarian
    • , Stephen H. Ogilvie
    • , Samuel G. Duyker
    • , Hubert Chevreau
    • , Vanessa K. Peterson
    •  &  Cameron J. Kepert
  • Nature Communications | Article | open

    Molecules can change their electronic properties when they are adsorbed on substrates, which can be useful for sensing and catalysis. Here, the authors use atomic force microscopy to show that the spin state of an iron complex can be changed upon displacing the molecule to different sites of a nitrogen-doped graphene

    • Bruno de la Torre
    • , Martin Švec
    • , Prokop Hapala
    • , Jesus Redondo
    • , Ondřej Krejčí
    • , Rabindranath Lo
    • , Debashree Manna
    • , Amrit Sarmah
    • , Dana Nachtigallová
    • , Jiří Tuček
    • , Piotr Błoński
    • , Michal Otyepka
    • , Radek Zbořil
    • , Pavel Hobza
    •  &  Pavel Jelínek
  • Nature Communications | Article | open

    Nitrogenase—whose cofactor consists of a metal–sulfur cluster—catalyzes the production of NH3 from N2, but designing metal–sulfur complexes capable of promoting this conversion remains challenging. Here, the authors report on the activation of N2 by a metal–sulfur cluster containing [Mo3S4Ti] cubes, demonstrating NH3 and N2H4 production.

    • Yasuhiro Ohki
    • , Keisuke Uchida
    • , Mizuki Tada
    • , Roger E. Cramer
    • , Takashi Ogura
    •  &  Takehiro Ohta
  • Nature Communications | Article | open

    The separation of high molecular weight polymers composed of the same number of monomeric units remains highly challenging. Here, the authors show that efficient separation and purification of mixtures of polymers that differ only by their terminal groups can be achieved through polymer threading in metal-organic framework channels.

    • Benjamin Le Ouay
    • , Chikara Watanabe
    • , Shuto Mochizuki
    • , Masayoshi Takayanagi
    • , Masataka Nagaoka
    • , Takashi Kitao
    •  &  Takashi Uemura
  • Nature Communications | Article | open

    Understanding quantum tunnelling of the magnetisation in single-molecule magnets is crucial for their potential application in information storage. Here the authors conduct a field- and temperature-dependent study of the magnetisation dynamics of a dysprosium-based SMM, finding four distinct relaxation processes that dominate in different regimes.

    • You-Song Ding
    • , Ke-Xin Yu
    • , Daniel Reta
    • , Fabrizio Ortu
    • , Richard E. P. Winpenny
    • , Yan-Zhen Zheng
    •  &  Nicholas F. Chilton
  • Nature Communications | Article | open

    Stimuli-responsive porous materials are attractive for a range of applications, but each material typically exhibits only one type of transformation. Here, the authors report on a metal–organic material that exhibits six distinct phases as a result of four types of structural transformation in response to different stimuli.

    • Mohana Shivanna
    • , Qing-Yuan Yang
    • , Alankriti Bajpai
    • , Ewa Patyk-Kazmierczak
    •  &  Michael J. Zaworotko
  • Nature Communications | Article | open

    Spin-crossover molecules offer a potential route towards molecular spintronics, but retaining the bistability of the spin state upon surface deposition is challenging. Here, the authors study the spin-crossover behaviours of an Fe(II) complex deposited on graphite, determining the scale limit at which cooperative spin switching becomes effective.

    • Lalminthang Kipgen
    • , Matthias Bernien
    • , Sascha Ossinger
    • , Fabian Nickel
    • , Andrew J. Britton
    • , Lucas M. Arruda
    • , Holger Naggert
    • , Chen Luo
    • , Christian Lotze
    • , Hanjo Ryll
    • , Florin Radu
    • , Enrico Schierle
    • , Eugen Weschke
    • , Felix Tuczek
    •  &  Wolfgang Kuch
  • Nature Communications | Article | open

    While polyhedral boron hydride complexes have found application in a number of diverse fields, the isolation of stable aluminium analogues remains highly challenging. Here, Jones and colleagues demonstrate that reduction of an amidinato-aluminum(III) hydride complex with magnesium(I) dimers affords stable aluminium(I) hydride compounds.

    • Simon J. Bonyhady
    • , David Collis
    • , Nicole Holzmann
    • , Alison J. Edwards
    • , Ross O. Piltz
    • , Gernot Frenking
    • , Andreas Stasch
    •  &  Cameron Jones
  • Nature Communications | Article | open

    Owing to the propensity for uranium(III) compounds to undergo disproportionation, uranium-element multiple bonds involving uranium(III) oxidation states remain rare. Here the authors report hexauranium-methanediide rings that formally contain uranium(III)- and uranium(IV)-methanediides supported by alternating halide and arene bridges.

    • Ashley J. Wooles
    • , David P. Mills
    • , Floriana Tuna
    • , Eric J. L. McInnes
    • , Gareth T. W. Law
    • , Adam J. Fuller
    • , Felipe Kremer
    • , Mark Ridgway
    • , William Lewis
    • , Laura Gagliardi
    • , Bess Vlaisavljevich
    •  &  Stephen T. Liddle
  • Nature Communications | Article | open

    Paramagnetic metal clusters with large ground spin states often possess attractive magnetic behaviors for information storage or solid-state cooling applications. Here, the authors design a giant {Ni21Gd20} cage, which using quantum monte carlo simulations they predict to possess a spin ground state approaching S = 91.

    • Wei-Peng Chen
    • , Jared Singleton
    • , Lei Qin
    • , Agustín Camón
    • , Larry Engelhardt
    • , Fernando Luis
    • , Richard E. P. Winpenny
    •  &  Yan-Zhen Zheng
  • Nature Communications | Article | open

    The recently introduced glass and liquid states of metal–organic frameworks (MOFs) provide opportunities to design and explore new properties for this class of material. Here, the authors show that a MOF liquid can be blended with another MOF component to produce domain-structured MOF glasses with single, tailorable glass transitions.

    • Louis Longley
    • , Sean M. Collins
    • , Chao Zhou
    • , Glen J. Smales
    • , Sarah E. Norman
    • , Nick J. Brownbill
    • , Christopher W. Ashling
    • , Philip A. Chater
    • , Robert Tovey
    • , Carola-Bibiane Schönlieb
    • , Thomas F. Headen
    • , Nicholas J. Terrill
    • , Yuanzheng Yue
    • , Andrew J. Smith
    • , Frédéric Blanc
    • , David A. Keen
    • , Paul A. Midgley
    •  &  Thomas D. Bennett
  • Nature Communications | Article | open

    Endowing metal–organic frameworks with both high electrical conductivity and magnetic ordering could make such materials useful for spintronics. Here the authors design a layer-stacking coronene-based 2D MOF that exhibits a semiconducting feature with an electrical conductivity of ~10 S cm−1 at 300 K, as well as ferromagnetism below ~20 K.

    • Renhao Dong
    • , Zhitao Zhang
    • , Diana C. Tranca
    • , Shengqiang Zhou
    • , Mingchao Wang
    • , Peter Adler
    • , Zhongquan Liao
    • , Feng Liu
    • , Yan Sun
    • , Wujun Shi
    • , Zhe Zhang
    • , Ehrenfried Zschech
    • , Stefan C. B. Mannsfeld
    • , Claudia Felser
    •  &  Xinliang Feng
  • Nature Communications | Article | open

    Owing to the energetic nature of N–N bonds, poly-nitrogen compounds are considered promising high energy density materials. Here, the authors synthesize three iron–nitrogen compounds at high pressure, including FeN4, which features polymeric nitrogen chains of [N42−]n units.

    • M. Bykov
    • , E. Bykova
    • , G. Aprilis
    • , K. Glazyrin
    • , E. Koemets
    • , I. Chuvashova
    • , I. Kupenko
    • , C. McCammon
    • , M. Mezouar
    • , V. Prakapenka
    • , H.-P. Liermann
    • , F. Tasnádi
    • , A. V. Ponomareva
    • , I. A. Abrikosov
    • , N. Dubrovinskaia
    •  &  L. Dubrovinsky
  • Nature Communications | Article | open

    While metal–carbon double bonds are common in transition metal chemistry and catalysis, unsupported uranium–carbon double bonds remain highly challenging to prepare. Here, the authors stabilize and characterize a U=C=U cluster containing unusually short, unsupported double bonds inside an Ih(7)-C80 fullerene cage.

    • Xingxing Zhang
    • , Wanlu Li
    • , Lai Feng
    • , Xin Chen
    • , Andreas Hansen
    • , Stefan Grimme
    • , Skye Fortier
    • , Dumitru-Claudiu Sergentu
    • , Thomas J. Duignan
    • , Jochen Autschbach
    • , Shuao Wang
    • , Yaofeng Wang
    • , Giorgios Velkos
    • , Alexey A. Popov
    • , Nabi Aghdassi
    • , Steffen Duhm
    • , Xiaohong Li
    • , Jun Li
    • , Luis Echegoyen
    • , W. H. Eugen Schwarz
    •  &  Ning Chen