Featured
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Tunable valence tautomerism in lanthanide–organic alloys
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
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Article |
A trivalent 4f complex with two bis-silylamide ligands displaying slow magnetic relaxation
A trivalent 4f cationic complex bearing two bis-silylamide ligands has been prepared that displays slow magnetic relaxation. The bulky ligands and weakly coordinating anion stabilize the pseudotrigonal geometry necessary to elicit strong ground-state magnetic anisotropy in this axially coordinated Yb(III) complex with well-localized charges.
- Dylan Errulat
- , Katie L. M. Harriman
- & Muralee Murugesu
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News & Views |
Molecular spins clock in
Electron spin relaxation, important in quantum information science, can be slowed down at clock transitions — which are insensitive to magnetic noise. It has now been shown that such transitions can be tuned, to high frequency, in rare-earth coordination complexes through control of s- and d-orbital mixing.
- Eric J. L. McInnes
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Article |
A 9.2-GHz clock transition in a Lu(II) molecular spin qubit arising from a 3,467-MHz hyperfine interaction
The s-orbital mixing into the spin-bearing d orbital associated with a molecular Lu(II) complex is shown to both reduce spin–orbit coupling and increase electron–nuclear hyperfine interactions, which substantially improves electron spin coherence. Combined with the potential to tune interactions through coordination chemistry, it makes this system attractive for quantum information applications.
- Krishnendu Kundu
- , Jessica R. K. White
- & Stephen Hill
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Article |
Switching the magnetic hysteresis of an [Feii–NC–Wv]-based coordination polymer by photoinduced reversible spin crossover
Photoinduced spin crossover offers a convenient handle on the spin states and magnetic interactions within a material, which is promising for the development of photoresponsive nanomagnets. Now, a Wv–CN–Feii-based coordination polymer has been prepared that behaves either as a single-chain magnet or as single-molecule magnets under different light irradiations. Its magnetic hysteresis can also be switched on and off.
- Liang Zhao
- , Yin-Shan Meng
- & Tao Liu
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Article |
Magnetic ordering through itinerant ferromagnetism in a metal–organic framework
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
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Article |
A metal–organic framework that exhibits CO2-induced transitions between paramagnetism and ferrimagnetism
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
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News & Views |
Taking titanium for a spin
Spin-1/2 kagome lattice antiferromagnets are geometrically frustrated materials poised to host yet-unobserved behaviours. Now, such a lattice has been prepared that shows no structural distortions and hosts its spin in the dxy orbital of d1 Ti3+ centres, rather than the more-widely investigated d9 Cu2+ ions.
- Kelsey A. Collins
- & Danna E. Freedman
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Article |
Synthesis of a d1-titanium fluoride kagome lattice antiferromagnet
The highly frustrated spin-1/2 kagome lattice antiferromagnet, predicted to exhibit unconventional magnetic behaviours, has remained difficult to synthesize without structural imperfections. Now, a d1-titanium fluoride kagome lattice antiferromagnet has been prepared in which there is only one crystallographically distinct Ti3+ site and one type of bridging fluoride, and it is shown to be a frustrated magnet with unusual magnetic properties.
- Ningxin Jiang
- , Arun Ramanathan
- & Henry S. La Pierre
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Vibrational coherences in manganese single-molecule magnets after ultrafast photoexcitation
Controlling single-molecule magnets (SMMs) with ultrashort laser pulses could be key to future data storage devices, however, the photophysics of SMMs is complex. Now, using a monomer model system, it has been shown that optical excitation of Mn(iii)-SMMs leads to a modulation of the Jahn–Teller distortion, which is important for its magnetic anisotropy.
- Florian Liedy
- , Julien Eng
- & J. Olof Johansson
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Observation of the asphericity of 4f-electron density and its relation to the magnetic anisotropy axis in single-molecule magnets
Gaining a better understanding of the complex electronic structure of single-molecule magnets is essential for their design and development. The 4f-electron density distribution of a dysprosium single-molecule magnet has now been experimentally determined using synchrotron diffraction data interpreted with a multipole model. The magnetic easy axes were recovered by analysis of the 4f-electron density shape, which is clearly oblate.
- Chen Gao
- , Alessandro Genoni
- & Jacob Overgaard
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Perspective |
Molecular spins for quantum computation
Spins in molecules provide a simple platform with which to encode a quantum bit (qubit), the elementary unit of future quantum computers. This Perspective discusses how chemistry can contribute to designing robust spin systems based, in particular, on mononuclear lanthanoid complexes.
- A. Gaita-Ariño
- , F. Luis
- & E. Coronado
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Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry
Layered coordination polymers are attractive for the preparation of advanced 2D materials but they are typically non-magnetic insulators. Now such a layered network, CrCl2(pyrazine)2, has been prepared that comprises a paramagnetic metal ion and a redox-active ligand. The material exhibits both magnetism — with a ferrimagnetic ground state — and high electrical conductivity.
- Kasper S. Pedersen
- , Panagiota Perlepe
- & Rodolphe Clérac
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News & Views |
Synthesis successes
Disentangling the chemistry and physics behind reported unconventional superconductivity and exotic magnetism in alkali-intercalated PAHs has remained problematic due to the lack of phase-pure samples. Two synthetic pathways have now remedied this issue, facilitating studies of cooperative electronic properties based on carbon π-electrons.
- Roser Valentí
- & Stephen M. Winter
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π-electron S = ½ quantum spin-liquid state in an ionic polyaromatic hydrocarbon
Cooperative electronic properties that arise purely from carbon π-electrons can lead to unconventional superconductivity and quantum magnetism. New packing architectures have now been established in two caesium-intercalated polyaromatic hydrocarbons, CsPhenanthrene and Cs2Phenanthrene, both strongly correlated multi-orbital Mott insulators. The frustrated magnetic topology in CsPhenanthrene also renders it a spin-½ quantum spin liquid candidate.
- Yasuhiro Takabayashi
- , Melita Menelaou
- & Kosmas Prassides
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Review Article |
Dynamic molecular crystals with switchable physical properties
Numerous dynamic molecular crystals whose physical properties can be switched by external stimuli have recently been developed. This Review discusses how the precise control of the electron, proton and molecular movement within the crystals through the application of external stimuli can lead to considerable changes in their properties.
- Osamu Sato
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News & Views |
Iron lines up
For more than a decade, single-molecule magnets have relied on multinuclear transition metal clusters and lanthanide compounds. Now, a mononuclear, two-coordinate iron(I) complex has shown that single transition metals can compete with the lanthanides when certain design principles from magnetochemistry are borne in mind.
- Eckhard Bill
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News & Views |
Uranyl steps in the ring
Uranium and manganese cations have been combined in a wheel-shaped supramolecular assembly that retains its magnetic spin state after the external field is removed, with a high barrier to its relaxation. This cluster supports recent predictions of the usefulness of the actinides in single-molecule magnetic devices.
- Polly L. Arnold
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Article |
Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier
A {U12Mn6} wheel-shaped cluster that has been assembled through cation–cation interactions exhibits single-molecule-magnet behaviour. Single-molecule magnets are promising for magnetic storage devices at the nanoscale, and the observation of magnetic bistability with an open hysteresis loop and high relaxation barrier in this 5f–3d complex suggests that uranium-based compounds could be useful components.
- Victor Mougel
- , Lucile Chatelain
- & Marinella Mazzanti
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News & Views |
The orientation is in the details
A detailed magnetic, structural and luminescence characterization unveils that what may have looked like mere details have a significant influence on the magnetic properties of a dysprosium complex.
- Muralee Murugesu
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News & Views |
A new spin on frustration
Solid-state science and technology in the twentieth century was defined by the transistor and the integrated circuit. Will the quest for a quantum spin liquid, which is inspired by theoretical and experimental advances, spawn the information technology of tomorrow?
- Kenneth R. Poeppelmeier
- & Masaki Azuma
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Light-induced spin-crossover magnet
In extended networks, light-induced magnetic ordering through spin change typically involves a charge-transfer mechanism, and thus a valence change of the magnetic metal centres. Now, such long-range ordering has been achieved in a three-dimensional metal–organic framework through the low-spin to high-spin transition of iron(II) centres, leading to a pronounced spontaneous magnetization.
- Shin-ichi Ohkoshi
- , Kenta Imoto
- & Hiroko Tokoro
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News & Views |
Uranium memory
A diuranium compound featuring an arene bridge shows single-molecule-magnet behaviour, which could arise from a mechanism different from the traditional 'super-exchange' spin coupling.
- Marinella Mazzanti
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Article |
Strong exchange and magnetic blocking in N23−-radical-bridged lanthanide complexes
Single-molecule magnets hold great promise for device miniaturization but the blocking temperatures at which they perform must first reach practical values. Now, the electronically diffuse N23− radical bridge has been shown to endow two di-lanthanide complexes with good magnetic properties — a di-gadolinium complex displays a strong magnetic coupling and its di-dysprosium analogue a high blocking temperature.
- Jeffrey D. Rinehart
- , Ming Fang
- & Jeffrey R. Long
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A delocalized arene-bridged diuranium single-molecule magnet
Single-molecule magnets (SMMs) are multinuclear clusters whose behaviour typically relies on intramolecular spin-coupling interactions between neighbouring metal ions. A diuranium–arene complex has now been prepared that shows behaviour characteristic of an SMM without relying on this type of superexchange mechanism. This may enable the construction of SMMs that maintain their magnetism at higher temperatures.
- David P. Mills
- , Fabrizio Moro
- & Stephen T. Liddle
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News & Views |
Spinning into control
Spin transitions are the most common mechanism for switching molecules between two distinct energy states, for uses as diverse as memory devices and displays. How the transition is triggered is crucial, and a pentanuclear cluster has now been reported in which the spin transition is promoted by redox transfer between different metal ions.
- Roberta Sessoli