Metal–organic frameworks articles within Nature Chemistry

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  • Article |

    Two-dimensional covalent organic frameworks (2D COFs) enable the construction of bespoke functional materials, but designing dynamic 2D COFs is challenging. Now it has been shown that perylene-diimide-based COFs can open and close their pores upon uptake or removal of guests, while fully retaining their crystalline long-range order. Moreover, the variable COF geometry enables stimuli-responsive optoelectronic properties.

    • Florian Auras
    • , Laura Ascherl
    •  & Thomas Bein

  • News & Views |

    X-ray diffraction analysis typically affords the static 3D structures of given compounds or materials, but to understand chemical processes, the visualization of fast structural changes is desirable. Time-resolved femtosecond crystallography has now been used to monitor the structural dynamics of a photoactive metal–organic framework.

    • Lauren E. Hatcher
    •  & Paul R. Raithby

  • Article
    | Open Access

    Time-resolved femtosecond crystallography (TR-SFX) is a powerful technique to monitor structural transitions in protein crystals at the atomic level, but its use in non-protein synthetic materials remains limited. Now TR-SFX has been used to visualize the structural dynamics of metal–organic frameworks, showing the potential of this tool to study the dynamic motion of crystalline porous materials.

    • Jaedong Kang
    • , Yunbeom Lee
    •  & Hyotcherl Ihee

  • Article |

    Valence tautomerism in lanthanide-based materials is rare. Now a one-dimensional samarium–pyrazine polymer has been shown to exhibit a temperature-induced hysteretic Sm(III)-to-Sm(II) reversible switch. The transition temperature is modulated in a 150 K window by alloying with Yb(II), presenting a strategy for developing new materials with chemically tunable magnetic switchability.

    • Maja A. Dunstan
    • , Anna S. Manvell
    •  & Kasper S. Pedersen

  • News & Views |

    The intentional interweaving of two different metal–organic framework (MOF) lattices could offer a strategy for combining the disparate properties of the two frameworks within a single MOF material. Now, the rational construction of such hetero-interpenetrated MOFs has been demonstrated.

    • Tendai Gadzikwa

  • Article |

    Interpenetration—in which two or more lattices are catenated—is common in metal–organic frameworks (MOFs). Now a deliberate synthesis of hetero-interpenetrated MOFs, with two distinct lattices, has been developed. It can combine the different properties of the two sublattices in one material, as demonstrated with chirality and catalytic activity, delivering an asymmetric catalyst.

    • David Perl
    • , Seok J. Lee
    •  & Shane G. Telfer

  • Article
    | Open Access

    Sorbent materials that reversibly transform between closed (non-porous) and open (porous) phases on the uptake and release of guests are relevant to gas storage and separation applications. Now, a coordination network has been prepared that exhibits gas-induced transformations between multiple non-porous phases. This phenomenon is attributed to subtle structural rearrangements that enable transient porosity.

    • Varvara I. Nikolayenko
    • , Dominic C. Castell
    •  & Michael J. Zaworotko

  • Article |

    The nitrogen reduction reaction is an extremely valuable but energy-intensive process. Now, a coordination polymer based on a [Zn–N2–Zn] unit has been shown to promote the formation of ammonia under ambient conditions by a photocatalytic reaction. The N2 moieties within the framework are reduced, creating unsaturated [Zn2+···Zn+] intermediates that are able to capture external N2 and sustain the cycle.

    • Yan Xiong
    • , Bang Li
    •  & Zhong Jin

  • Review Article |

    The light-driven conversion of abundant resources such as CO2 and H2O into chemical fuels for energy storage is crucial to end our dependence on fossil fuels. This Review highlights how molecular catalysts and photosensitizers can be grafted onto metal–organic frameworks to combine the advantages of both classes of compounds. Different synthetic strategies are discussed, along with their advantages and limitations.

    • P. M. Stanley
    • , J. Haimerl
    •  & J. Warnan

  • Perspective |

    Hydrogen, which possesses the highest gravimetric energy density of any energy carrier, is attractive for both mobile and stationary power, but its low volumetric energy density poses major storage and transport challenges. This Perspective delineates potential use cases and defines the challenges facing the development of materials for efficient hydrogen storage.

    • Mark D. Allendorf
    • , Vitalie Stavila
    •  & Tom Autrey

  • Article |

    Flexible metal–organic frameworks (MOFs) in which guest uptake and release occur above certain threshold pressures are attractive adsorbents. Now, the gated sorption behaviour of such a zinc-based mixed-ligand MOF has been tuned to match the narrow temperature and pressure range required for safe, efficient acetylene storage by adjusting the ratio of two different functional groups on its benzenedicarboxylate ligands.

    • Mickaele Bonneau
    • , Christophe Lavenn
    •  & Susumu Kitagawa

  • News & Views |

    The adsorption of molecules onto a surface from solution generally proceeds spontaneously by means of an equilibrium process. Now, it has been shown that macrocycles can be pumped onto a MOF substrate through the formation of mechanical bonds in a ratcheting mechanism that results in an out-of-equilibrium state.

    • Liang Zhang

  • News & Views |

    Among the tens of thousands of reported hybrid organic–inorganic crystals, only a small fraction of them are known to form a stable liquid upon heating. Now, a family of hybrid perovskites is shown to melt and, upon cooling, form glasses with a compelling combination of properties.

    • Morten M. Smedskjaer
    •  & Søren S. Sørensen

  • Article |

    Oxidation states help chemists to understand the bonding, properties and reactivity of compounds, but they can be difficult to determine for metal ions in extended crystalline materials. Now, oxidation states manually assigned to metal–organic frameworks have been harvested from the Cambridge Structural Database and used to build a machine-learning model that predicts oxidation states in metal–organic frameworks with good accuracy.

    • Kevin Maik Jablonka
    • , Daniele Ongari
    •  & Berend Smit

  • Article |

    A series of dicyanamide-based hybrid organic–inorganic perovskite structures has been shown to melt at temperatures below 300 °C. On melt-quenching, they form glasses that possess coordination bonding and show very low thermal conductivities and moderate electrical conductivities as well as polymer-like thermomechanical properties.

    • Bikash Kumar Shaw
    • , Ashlea R. Hughes
    •  & Thomas D. Bennett

  • Article |

    The development of metal–organic magnets that combine tunable magnetic properties with other desirable physical properties remains challenging despite numerous potential applications. Now, a mixed-valent chromium–triazolate material has been prepared that exhibits itinerant ferromagnetism with a magnetic ordering temperature of 225 K, a high conductivity and large negative magnetoresistance (23%).

    • Jesse G. Park
    • , Brianna A. Collins
    •  & Jeffrey R. Long

  • Article |

    A metal–organic framework (MOF) has been prepared that features dynamic rotors embedded within its crystalline lattice. The dipolar F2-functionalized carboxylate linkers—rapidly rotating at room temperature—show correlated behaviour upon cooling, converting the paraelectric MOF into an ordered antiferroelectric one below 100 K.

    • Y.-S. Su
    • , E. S. Lamb
    •  & S. E. Brown

  • Article |

    Some metal–organic frameworks (MOFs) can promote photocatalytic hydrogen evolution and others can facilitate water oxidation, but it is difficult to combine them into a single system. Now, by confining MOFs that can promote each half-reaction within the hydrophobic and hydrophilic regions of a liposome to avoid the fast recombination of photo-generated charges, evidence for water splitting has been obtained.

    • Huihui Hu
    • , Zhiye Wang
    •  & Cheng Wang

  • Article |

    Metal–organic frameworks (MOFs) can combine porosity and magnetic order within their lattice, which makes them attractive for the development of stimuli-responsive magnets. Now, a MOF has been prepared that converts from a ferrimagnet to a paramagnet with CO2 uptake, and returns to the ferrimagnetic state on releasing CO2.

    • Jun Zhang
    • , Wataru Kosaka
    •  & Hitoshi Miyasaka

  • Article |

    Molecular rotors have been engineered within the bicyclopentane–dicarboxylate struts of a metal–organic framework—the bicyclic unit is the rotator and the carboxylate groups serve as the stator. In a zinc-based metal–organic framework, the crossed conformation of the strut–metal nodes enables fast rotation of the bicyclic moiety, but in the corresponding zirconium metal–organic framework a change in the conformation results in much slower rotation.

    • Jacopo Perego
    • , Silvia Bracco
    •  & Piero Sozzani

  • Article |

    A material based on a three-dimensional –Fe–N≡C–Mo– anionic framework that hosts a Cs+ cation in every other pore has been shown to exhibit superionic conductivity, despite its polar crystal structure. It also exhibits second harmonic generation (SHG)—usually observed in insulators—and its ionic conductivity was reversibly altered under light irradiation.

    • Shin-ichi Ohkoshi
    • , Kosuke Nakagawa
    •  & Asuka Namai

  • Article |

    A disordered metal–organic framework converts into a more porous, crystalline phase within 40 s following solvent exchange and desolvation. The rapid domino rearrangement of the whole lattice, which involves carboxylate migration on coordinatively unsaturated metal sites, is accompanied by a substantial increase in surface area.

    • Sheng-Han Lo
    • , Liang Feng
    •  & Hong-Cai Zhou

  • Article |

    A stable zinc-based metal–organic framework known to retain its porosity and crystallinity after exposure to moisture has been shown to undergo structural changes at the molecular level on adsorbing water. This dynamic and reversible response to the presence of water, including the rearrangement of bonds, is suggested to be the reason for the hydrolytic stability of this particular metal–organic framework.

    • Nicholas C. Burtch
    • , Ian M. Walton
    •  & Krista S. Walton

  • Article |

    High electrical conductivities in metal–organic frameworks—attractive for applications in sensing and energy storage—typically arise in layered MOFs from metal–ligand bonds with strong covalent character. Now, lanthanide-based MOFs have shown high out-of-plane conductivities originating instead from the π-stacking of organic ligands.

    • Grigorii Skorupskii
    • , Benjamin A. Trump
    •  & Mircea Dincă

  • Article |

    Nitrogen oxides are major air pollutants; capture and abatement technologies exist but they typically involve toxic species or precious-metal catalysts. Now, a metal–organic framework has been shown to store NO2 dimers selectively, and to separate NO2 from other gases under wet conditions. Treatment with water in air leads to conversion of NO2 into HNO3—an important feedstock for fertilizer production—with full recovery of the host.

    • Jiangnan Li
    • , Xue Han
    •  & Sihai Yang

  • Article |

    Gas sorption studies in porous materials typically reflect their overall gas uptake. Now, using a ‘gas adsorption crystallography’ method, the gas adsorption isotherms of two metal–organic frameworks (MOFs) have been quantitatively decomposed into sub-isotherms that reflect the pore-filling behaviour of various guests in the different types of pores present in the MOFs.

    • Hae Sung Cho
    • , Jingjing Yang
    •  & Osamu Terasaki

  • Article |

    Structural defects are known to exist in metal–organic frameworks (MOFs), and to affect the materials’ properties, but their exact structures have remained difficult to determine. Now, missing-linker and missing-cluster defects have been observed in a MOF using low-dose transmission electron microscopy, enabling their distributions, evolutions during crystallization and effects on the material’s catalytic activity to be explored.

    • Lingmei Liu
    • , Zhijie Chen
    •  & Yu Han

  • Article |

    Some porous coordination polymers (PCPs) are known to be flexible and guest-responsive. Now, the guest-induced sharp, reversible structural transformation of the surface of a single-crystalline PCP has been visualized by in situ liquid-phase atomic force microscopy. This local response occurred at a guest concentration that was too low to trigger changes to the bulk crystal.

    • Nobuhiko Hosono
    • , Aya Terashima
    •  & Susumu Kitagawa

  • Article |

    Solid acid heterogeneous catalysts are widely used in industrial chemical processes, but understanding the exact molecular structures responsible for catalytic activity has proved difficult. Now, the structure of the strong Brønsted acid site for a sulfated zirconium-based metal–organic framework has been shown to consist of a specific arrangement of adsorbed water and sulfate moieties on the zirconium clusters.

    • Christopher A. Trickett
    • , Thomas M. Osborn Popp
    •  & Omar M. Yaghi

  • News & Views |

    The applicability of metal-organic frameworks (MOFs) — in spite of their obvious potential — is hindered by stability issues, in particular towards water. Now, a ‘crumple zone’ concept has been proposed in which the presence of sacrificial bonds protects a MOF without significantly altering its structure or functionality.

    • Jürgen Senker

  • Article |

    The promise shown by metal–organic frameworks for various applications is somewhat dampened by their instability towards water. Now, an activated MOF has shown good hydrolytic stability owing to the presence of weak, sacrificial coordination bonds that act as a ‘crumple zone’. On hydration, these weak bonds are cleaved preferentially to stronger coordination bonds that hold the MOF together.

    • Lauren N. McHugh
    • , Matthew J. McPherson
    •  & Russell E. Morris

  • Article |

    Colloidal particles of metal–organic frameworks (ZIF-8 and UiO-66) with different polyhedral shapes can self-assemble into well-ordered, porous three-dimensional superstructures. These superstructures function as photonic crystals, with a photonic band gap that depends on the size of the MOF particles and shifts upon the sorption of guests within their pores.

    • Civan Avci
    • , Inhar Imaz
    •  & Daniel Maspoch

  • Article |

    Breathing metal–organic frameworks (MOFs) are functional materials whose molecular-scale pores can reversibly open and close. In contrast to typical defined structural transitions, continuous breathing has now been observed for a diamondoid MOF. Removal of two different solvents leads to two desolvated MOF polymorphs with dramatically different porosities and gas uptake properties, including CO2/CH4 selectivities. Partial desolvation introduces pressure-gated CO2 adsorption.

    • Elliot J. Carrington
    • , Craig A. McAnally
    •  & Lee Brammer

  • Perspective |

    Although metal–organic frameworks are often seen as rigid crystalline structures, there is growing evidence that large-scale flexibility, the presence of defects, and long-range disorder are not the exception, but rather the norm. Here we propose that these concepts are inescapably intertwined, and the interfaces between them offer prospects for enhancement of materials' functionalities.

    • Thomas D. Bennett
    • , Anthony K. Cheetham
    •  & François-Xavier Coudert

  • Editorial |

    Taking chemical technology from the bench to the consumer is a formidable challenge, but it is how research can ultimately benefit wider society. Companies are now beginning to incorporate metal–organic frameworks into commercial products, heralding a new era for the field.

  • Interview |

    Omar Farha (Chief Science Officer & technical founder) and Ben Hernandez (Chief Executive Officer) of NuMat Technologies, talk to Nature Chemistry about the release of one of the first MOF-based commercial products and the challenges the journey posed.

    • Thomas Faust

  • News & Views |

    The calcination of metal–organic framework (MOF) precursors is promising for the preparation of nanoscale carbon materials, but the resulting morphologies have remained limited. Now, controlling the growth of precursor MOFs has enabled 1D carbon nanorods to be fabricated — these can then be readily unravelled into 2D graphene nanoribbons.

    • Jing Tang
    •  & Yusuke Yamauchi

  • Article |

    A rod-shaped metal–organic framework can be converted into one-dimensional carbon nanorods through a catalyst-free thermal transformation in which the morphology of the material is preserved. The as-synthesized nanorods can be unravelled to form 2–6-layer graphene nanoribbons by ultrasonication in the presence of KOH, followed by thermal activation.

    • Pradip Pachfule
    • , Dhanraj Shinde
    •  & Qiang Xu

  • News & Views |

    The properties of metal–organic frameworks — promising for a myriad of applications — can be commonly tuned by judicious choice of the building blocks used to prepare the material. Now, simply downsizing a rigid, non-porous MOF to a thin film has been shown to endow it with dynamic, gate-opening-type guest uptake behaviour.

    • Christopher J. Sumby

  • Article |

    Covalent organic frameworks (COFs) are attractive multifunctional porous materials that can be generated with atomic precision. However, endowing them with long-range order—desirable for applications—has remained challenging. Now, propeller-shaped building units have been used that allow consecutive layers to lock in position, resulting in highly crystalline COFs.

    • Laura Ascherl
    • , Torben Sick
    •  & Thomas Bein

  • Article |

    Interpenetration of metal–organic frameworks (MOFs) is a common phenomenon, in which a structure consists of two or more identical, entangled sub-lattices. Now, MOFs with variable, fractional degrees of occupancy of one of two sub-lattices have been prepared. The extent of interpenetration can be controlled either during synthesis or by autocatenation, a framework rearrangement process.

    • Alan Ferguson
    • , Lujia Liu
    •  & Shane G. Telfer

  • Article |

    Highly compressible crystalline materials typically rely on the high compressibility of their chemical bonds. Now, a family of LnFe(CN)6 frameworks (Ln = Ho, Lu or Y) has been shown to exhibit pronounced volumetric and linear compressibilities through a spring-and-gear mechanism instead, in which a torsionally flexible LnN6 unit twists reversibly under pressure.

    • Samuel G. Duyker
    • , Vanessa K. Peterson
    •  & Cameron J. Kepert

  • News & Views |

    Incorporating mechanically interlocked molecular shuttles within a metal–organic framework that has enough free space in the crystal lattice to permit volume-conserving translational motion sets the stage for defect-free molecular-electronic device fabrication and more.

    • Mark A. Olson

  • Article |

    The piston-like, translational motion of a molecular shuttle — a process that is fundamental to many mechanically interlocked molecular switches and machines — has now been demonstrated to occur inside the highly organized and dense structure (containing approximately 1021 shuttles per cm3) of a metal–organic framework material.

    • Kelong Zhu
    • , Christopher A. O'Keefe
    •  & Stephen J. Loeb

  • News & Views |

    Membranes are key components for the removal of greenhouse gases during fuel generation processes, such as hydrogen production, but simultaneous permeability and selectivity is difficult to obtain. This has now been achieved in ultrathin membranes that use the size-selective porosity of metal–organic frameworks to separate CO2 from H2.

    • Tina M. Nenoff

  • Article |

    Gas sorption and separation in porous materials is dependent on the host–guest binding within any given system. Now, the molecular details of cooperative binding between small hydrocarbons and a metal–organic framework, NOTT-300, at multiple sites have been elucidated by complementary scattering and diffraction techniques. This material is also capable of separating C1 and C2 hydrocarbons under ambient conditions.

    • Sihai Yang
    • , Anibal J. Ramirez-Cuesta
    •  & Martin Schröder

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