Metal-organic Magnets Research Articles

Self-Assembled Tetranuclear Square Complex of Chromium(III) Bridged by Radical Pyrazine: A Molecular Model for Metal-Organic Magnets.

The attractive electronic properties of metal-pyrazine materials─electrical conductivity, magnetic order, and strong magnetic coupling─can be tuned in a wide range depending on the metal employed, as well as its ligand-imposed redox environment. Using solvent-directed synthesis to control the dimensionality of such systems, a discrete tetranuclear chromium(III) complex, exhibiting a rare example of bridging radical pyrazine, has been prepared from chromium(II) triflate and neutral pyrazine. The strong antiferromagnetic interaction between CrIII (S = 3/2) and radical pyrazine (S = 1/2) spins, theoretically estimated at about -932 K, leads to a thermally isolated ST = 4 ground state, which remains the only populated state observable even at room temperature.

Controlling Noncollinear Ferromagnetism in van der Waals Metal-Organic Magnets.

Van der Waals (vdW) magnets both allow exploration of fundamental 2D physics and offer a route toward exploiting magnetism in next generation information technology, but vdW magnets with complex, noncollinear spin textures are currently rare. We report here the syntheses, crystal structures, magnetic properties and magnetic ground states of four bulk vdW metal-organic magnets (MOMs): FeCl2(pym), FeCl2(btd), NiCl2(pym), and NiCl2(btd), pym = pyrimidine and btd = 2,1,3-benzothiadiazole. Using a combination of neutron diffraction and bulk magnetometry we show that these materials are noncollinear magnets. Although only NiCl2(btd) has a ferromagnetic ground state, we demonstrate that low-field hysteretic metamagnetic transitions produce states with net magnetization in zero-field and high coercivities for FeCl2(pym) and NiCl2(pym). By combining our bulk magnetic data with diffuse scattering analysis and broken-symmetry density-functional calculations, we probe the magnetic superexchange interactions, which when combined with symmetry analysis allow us to suggest design principles for future noncollinear vdW MOMs. These materials, if delaminated, would prove an interesting new family of 2D magnets.

Ligand solid-solution tuning of magnetic and mechanical properties of the van der Waals metal-organic magnet NiCl2(btd)1-x(bod)x.

Van der Waals (vdW) magnets offer unique opportunities for exploring magnetism in the 2D limit. Metal-organic magnets (MOM) are of particular interest as the functionalisation of organic ligands can control their physical properties. Here, we demonstrate tuning of mechanical and magnetic function of a noncollinear vdW ferromagnet, NiCl2(btd) (btd = 2,1,3-benzothiadiazole), through creating solid-solutions with the oxygen-substituted analogue ligand 2,1,3-benzoxadiazole (bod). We synthesise NiCl2(btd)1-x(bod)x up to x = 0.33, above which we find mixtures primarily composed of 1D NiCl2(bod)2. Magnetometry reveals bod incorporation reduces the coercivity significantly (up to 60%), without altering the ordering temperatures. High pressure synchrotron diffraction measurements up to 0.4 GPa demonstrate that the stiffest axis is the b axis, through the Ni-N-(O/S)-N-Ni bonds, and the softest is the interlayer direction. Doping with bod fine-tunes this compressibility, softening the layers, but stiffening the interlayer axis. This demonstrates that substitution of organic ligands in vdW MOMs can be used to realise targeted magnetic and mechanical properties.

Low-Dimensional Metal-Organic Magnets as a Route toward the S = 2 Haldane Phase.

Metal-organic magnets (MOMs), modular magnetic materials where metal atoms are connected by organic linkers, are promising candidates for next-generation quantum technologies. MOMs readily form low-dimensional structures and so are ideal systems to realize physical examples of key quantum models, including the Haldane phase, where a topological excitation gap occurs in integer-spin antiferromagnetic (AFM) chains. Thus, far the Haldane phase has only been identified for S = 1, with S ≥ 2 still unrealized because the larger spin imposes more stringent requirements on the magnetic interactions. Here, we report the structure and magnetic properties of CrCl2(pym) (pym = pyrimidine), a new quasi-1D S = 2 AFM MOM. We show, using X-ray and neutron diffraction, bulk property measurements, density-functional theory calculations, and inelastic neutron spectroscopy (INS), that CrCl2(pym) consists of AFM CrCl2 spin chains (J1 = -1.13(4) meV) which are weakly ferromagnetically coupled through bridging pym (J2 = 0.10(2) meV), with easy-axis anisotropy (D = -0.15(3) meV). We find that, although small compared to J1, these additional interactions are sufficient to prevent observation of the Haldane phase in this material. Nevertheless, the proximity to the Haldane phase together with the modularity of MOMs suggests that layered Cr(II) MOMs are a promising family to search for the elusive S = 2 Haldane phase.

Magnetic ordering through itinerant ferromagnetism in a metal-organic framework.

Materials that combine magnetic order with other desirable physical attributes could find transformative applications in spintronics, quantum sensing, low-density magnets and gas separations. Among potential multifunctional magnetic materials, metal-organic frameworks, in particular, bear structures that offer intrinsic porosity, vast chemical and structural programmability, and the tunability of electronic properties. Nevertheless, magnetic order within metal-organic frameworks has generally been limited to low temperatures, owing largely to challenges in creating a strong magnetic exchange. Here we employ the phenomenon of itinerant ferromagnetism to realize magnetic ordering at TC = 225 K in a mixed-valence chromium(II/III) triazolate compound, which represents the highest ferromagnetic ordering temperature yet observed in a metal-organic framework. The itinerant ferromagnetism proceeds through a double-exchange mechanism, which results in a barrierless charge transport below the Curie temperature and a large negative magnetoresistance of 23% at 5 K. These observations suggest applications for double-exchange-based coordination solids in the emergent fields of magnetoelectrics and spintronics.

Metal-organic magnets with large coercivity and ordering temperatures up to 242°C.

Magnets derived from inorganic materials (e.g., oxides, rare-earth-based, and intermetallic compounds) are key components of modern technological applications. Despite considerable success in a broad range of applications, these inorganic magnets suffer several drawbacks, including energetically expensive fabrication, limited availability of certain constituent elements, high density, and poor scope for chemical tunability. A promising design strategy for next-generation magnets relies on the versatile coordination chemistry of abundant metal ions and inexpensive organic ligands. Following this approach, we report the general, simple, and efficient synthesis of lightweight, molecule-based magnets by postsynthetic reduction of preassembled coordination networks that incorporate chromium metal ions and pyrazine building blocks. The resulting metal-organic ferrimagnets feature critical temperatures up to 242°C and a 7500-oersted room-temperature coercivity.

Spin wave excitations of magnetic metalorganic materials

The Organic Materials Database (OMDB) is an open database hosting about 22,000 electronic band structures, density of states and other properties for stable and previously synthesized 3-dimensional organic crystals. The web interface of the OMDB offers various search tools for the identification of novel functional materials such as band structure pattern matching and density of states similarity search. In this work the OMDB is extended to include magnetic excitation properties. For inelastic neutron scattering we focus on the dynamical structure factor $S(\mathbf{q},\omega)$ which contains information on the excitation modes of the material. We introduce a new dataset containing atomic magnetic moments and Heisenberg exchange parameters for which we calculate the spin wave spectra and dynamic structure factor with linear spin wave theory and atomistic spin dynamics. We thus develop the materials informatics tools to identify novel functional organic and metalorganic magnets.

Metal-Organic Framework Magnets.

Metal-organic frameworks represent the ultimate chemical platform on which to develop a new generation of designer magnets. In contrast to the inorganic solids that have dominated permanent magnet technology for decades, metal-organic frameworks offer numerous advantages, most notably the nearly infinite chemical space through which to synthesize predesigned and tunable structures with controllable properties. Moreover, the presence of a rigid, crystalline structure based on organic linkers enables the potential for permanent porosity and postsynthetic chemical modification of the inorganic and organic components. Despite these attributes, the realization of metal-organic magnets with high ordering temperatures represents a formidable challenge, owing largely to the typically weak magnetic exchange coupling mediated through organic linkers. Nevertheless, recent years have seen a number of exciting advances involving frameworks based on a wide range of metal ions and organic linkers. This review provides a survey of structurally characterized metal-organic frameworks that have been shown to exhibit magnetic order. Section 1 outlines the need for new magnets and the potential role of metal-organic frameworks toward that end, and it briefly introduces the classes of magnets and the experimental methods used to characterize them. Section 2 describes early milestones and key advances in metal-organic magnet research that laid the foundation for structurally characterized metal-organic framework magnets. Sections 3 and 4 then outline the literature of metal-organic framework magnets based on diamagnetic and radical organic linkers, respectively. Finally, Section 5 concludes with some potential strategies for increasing the ordering temperatures of metal-organic framework magnets while maintaining structural integrity and additional function.

Dimensional reduction by pressure in the magnetic framework material CuF2(D2O)2 (pyz): From spin-wave to spinon excitations

Metal organic magnets have enormous potential to host a variety of electronic and magnetic phases that originate from a strong interplay between the spin, orbital and lattice degrees of freedom. We control this interplay in the quantum magnet CuF$_2$(D$_2$O)$_2$pyz by using high pressure to drive the system through a structural and magnetic phase transition. Using neutron scattering, we show that the low pressure state, which hosts a two-dimensional square lattice with spin-wave excitations and a dominant exchange coupling of 0.89 meV, transforms at high pressure into a one-dimensional spin-chain hallmarked by a spinon continuum and a reduced exchange interaction of 0.43 meV. This direct microscopic observation of a magnetic dimensional crossover as a function of pressure opens up new possibilities for studying the evolution of fractionalised excitations in low dimensional quantum magnets and eventually pressure-controlled metal--insulator transitions.

Nonlinear spin excitations in chiral magnetic solids

Comparative analysis of nonlinear spin excitations in inorganic and metal-organic magnets was performed. The properties of nonlinear magnetic excitations in molecular magnets were established: differences in the remagnetization modes of chiral and racemic crystals, effect of chirality of crystals on the soliton spin excitations, decrease in the threshold microwave power at transition to the nonlinear ferromagnetic resonance mode. It is shown that the domain wall dynamics and development of Suhl’s instability provide additional information on the microscopic mechanisms of magnetization of molecular metal-organic magnets in comparison with inorganic magnets.

Ordered arrays of metal–organic magnets at surfaces

We report here on the molecular self-assembly of 7, 7′, 8, 8′ tetracyanoquinodimethane (TCNQ) (schematic representation of the molecule on figure 1(b)) on a single-crystal Cu(111) surface, followed by deposition of Fe and Mn, and on the formation of an ordered metal–organic coordination network of Fe (or Mn)–TCNQ units, which contains magnetic ions separated by 0.9 nm.

3D Long-Range Magnetic Ordering in Layered Metal–Hydroxide Triangular Lattices 25 Å Apart

The synthesis, characterization, and magnetic properties of the layered compounds, Cu2(OH)3(C12H25SO3)·H2O, Ni2(OH)3(C12H25SO3)·H2O, and Co5(OH)8(C12H25SO3)2·5H2O, with a triangular magnetic lattice are reported. The interlayer distances are 23.8 (Cu), 23.0 (Ni), and 25.8 Å (Co). Long-range ferromagnetic (Ni) and ferrimagnetic (Co) ordering are observed with Curie temperatures of 18 (Ni) and 50K (Co). The coercive fields are 400 (Ni) and 19,000 Oe (Co), the latter being among the hardest metal–organic magnets. The long-range ordering is interpreted as being due to dipolar interaction between layers with large effective moments as a consequence of precursor short-range intralayer interactions. The large coercive field is interpreted as resulting from a synergy of crystalline shape, surface, and single ion anisotropies.