Chiral Magnetism and Organic Magnets – Multifunctional Magnetic Molecular Materials

Background and current status

Research on magnetic molecular materials has received strong attention in the last years for many reasons. In particular, molecular engineering offers far more possibilities than traditional inorganic and metallic synthetic routes to design multifunctional materials, often also considered smart materials, with the desired physical properties for specific applications. Examples are magnets with non-linear optical behaviour, strongly anisotropic conducting magnets, or the potential that single molecule magnets offer to develop devices for ultra high density data storage.

Among these materials, chiral materials generally show interesting physical phenomena related to the breaking of spatial symmetry, and open the possibility of combining electrical, optical and other properties in a single material, thus providing new multifunctional properties.

In addition to their scientific interest, materials of this category may also open an area for new applications as it has been proposed regarding the crucial role that magnetic chirality can play in spintronic devices where spin and electron charge are used for data transmission.

Thus it is clear that chirality, in general sense, will be closely related with multifunctionality. However there are not so many examples of molecular materials with coupled magnetic and electrical properties, which would attract much interest from the point of view of spintronic devices. Some of the described examples are the multiferroic molecular materials, in which magnetic (non collinear) and electrical order coexist, opening a vast world of technological perspectives, especially when the magneto-electric coupling is important.

For example, there are theoretical predictions about multiferroic ordering in compounds based on p-NPNN radicals in triangular topology networks, or new phenomenology (3D spin liquid) is anticipated in compounds with hyper-Kagome topology based on organic radicals. Obviously, in these purely organic magnets the origin of magnetic chirality, if any, would be related to the concept of magnetic frustration, as they are highly isotropic systems

Recent achievements

First hybrid/molecular Multiferroic

Although the (NH4)2FeCl5H2O was known for a long time, it had not been described as molecular multiferroic materials with a cycloidal magnetic structure until recently by M4. It is the first example of a hybrid multiferroic compound.

2D or 3D networks of SMM

It is noteworthy that our works on [Co4(citrate)4] clusters combine their SMM behaviour with 2D and 3D networks of magnetic centers (with high anisotropy) which gives rise to a modular magnetic behavior.

Organic radicals magnetism

Purely quantum ½ spin AF longe range order behaviour was observed in a "honeycomb" network based on the new biradicals F4BIPBNN by the group M4. The highest ordering temperature found for a purely organic magnet is another highlight of M4

Chiral Soliton Lattices

The phase diagram of helical monoaxial magnets has been determined for any applied magnetic field direction and any temperature. These predictions has been recently verified experimentally.

New Skyrmionic phases in cubic helimagnets

The effect of thermal fluctuations, predicted in 2017 the existence of a new skyrmionic phase at low temperature in chiral cubic magnets (MnSi, FeGe, etc ...) that has recently been discovered experimentally.

Present Goals

From the previous examples it can be presumed that the study and control of the non-colinear regime in magnetism, which arises from different origins (magnetic anisotropy, antisymmetric interaction Dzyaloshinskii-Moriya (DM), magnetic frustration, interaction competition, etc …), is a current technological issue.

The General Objective proposed in this project consists of the fundamental study (both experimental and theoretical) of the required ingredients (magnetic interactions, anisotropy and frustration) to control and generate magnetic chirality in relevant technological materials

Multi-ferroicity in molecular hybrid solids.

The final objective is to deep in the knowledge of these materials and their interaction mechanisms in order to open the possibility of designing new materials with improved magneto-electric coupling and higher ordering temperatures.

Magnetic chirality induced by DM antisymmetric interactions and magnetic anisotropy.

We plan to study, both theoretical and experimental, the role of the DM antisymmetric interaction, the anisotropy and the role of thermal fluctuations, on cubic magnets, monoaxial magnets, and 0-Dimensional systems (SMM).

Magnetic chirality induced by frustration in purely organic molecular magnets.

Here we intend to investigate the potential of purely organic magnetic molecular materials in order to generate and control magnetic chirality induced by only by frustration. There are interesting theoretical predictions on the appearance of multiferroicity, spin-ice behaviour, etc...

Magnonics in chiral magnets

CSIC (PIE-201960E080) (2020-2022)

Deeper exploration of the reciprocal space of MnSi at low temperatures to search for new magnetic textures

GIMRT (Institute for Materials Research Tohoku University), (2020-21)

Magnetic chirality induced by frustration in purely organic molecular magnets

GIMRT (Institute for Materials Research Tohoku University), (2019-20)

Quiralidad Magnética En Materiales Moleculares Magnéticos y Multifuncionales (ChiMag)

PGC-2018-099024-B-I00 MICIU (2019 – 2021)

Preparación y estudio de Materiales Magnéticos Multifuncionales de carácter Molecular

Gobierno de Aragón – Gr. Consolidado E11_R17 (2017-19)

Chirality and frustration in magnetic materials

CSIC (I-LINK) (2017-2018)

Materiales moleculares magnéticos multifuncionales para conducción en cristales flexibles y control de quiralidad magnética

MAT-2015-68200-C2-2-P (M4c2m) Ministerio de Economía y Competitividad (2016-2018)

Highlights

Scattering of spin waves by a Bloch domain wall: Effect of the dipolar interaction.

Victor Laliena, Athanasios Athanasopoulos and Javier Campo.

Background and current status

Recent achievements

First hybrid/molecular Multiferroic

2D or 3D networks of SMM

Organic radicals magnetism

Chiral Soliton Lattices

New Skyrmionic phases in cubic helimagnets

Present Goals

Multi-ferroicity in molecular hybrid solids.

Magnetic chirality induced by DM antisymmetric interactions and magnetic anisotropy.

Magnetic chirality induced by frustration in purely organic molecular magnets.

Last projects

Magnonics in chiral magnets

Deeper exploration of the reciprocal space of MnSi at low temperatures to search for new magnetic textures

Magnetic chirality induced by frustration in purely organic molecular magnets

Quiralidad Magnética En Materiales Moleculares Magnéticos y Multifuncionales (ChiMag)

Preparación y estudio de Materiales Magnéticos Multifuncionales de carácter Molecular

Chirality and frustration in magnetic materials

Materiales moleculares magnéticos multifuncionales para conducción en cristales flexibles y control de quiralidad magnética

Highlights

Scattering of spin waves by a Bloch domain wall: Effect of the dipolar interaction.

New magnetic intermediate state, “B-phase,” in the cubic chiral magnet MnSi

Magnonic Goos-Hänchen effect induced by one dimensional solitons

Metastability and Creation of single chiral soliton states in monoaxial helimagnets

Large magnetocaloric effect in EuGd2O4 and EuDy2O4

Stability of Ag(III) towards Halides in Organosilver(III) Complexes

A novel method to obtain integral parameters of the orientation distribution function of textured polycrystals from wavelength-resolved neutron transmission spectra

Efficient Brownian oscillators and nanoheaters based on gallium-doped e-Fe2O3†

A new twist on an old ligand: a [Mn16] double square wheel and a [Mn10] contorted wheel

Building C(sp3) Molecular Complexity on 2,2’-Bipyridine and 1,10-Phenanthroline in Rhenium Tricarbonyl Complexes

Field induced slow magnetic relaxation in a zig-zag chain-like Dy(III) complex with the ligand o-phenylenedioxydiacetato

On new solvatomorphs of the metalloligand [Ni(o-van-en)]

Intermediate magnetic phase of the magnetoelectric compound (Ca,Sr)BaCo4O7 described with the superspace formalism

Dynamics of chiral solitons driven by polarized currents in monoaxial helimagnets

Design and optimization of a magnet for magnetocaloric refrigeration.

Lanthanide Luminescence to Mimic Molecular Logic and Computing through Physical Inputs.

Switching of the Chiral Magnetic Domains in the Hybrid Molecular/Inorganic Multiferroic (ND4)(2)[FeCl5(D2O)].

Molecular nanoclusters as magnetic refrigerants: The case of Fe-14 with very large spin ground-state.

Thermometry at the nanoscale.

Rational Electrostatic Design of Easy-Axis Magnetic Anisotropy in a Zn-II-Dy-III-Zn-II Single-Molecule Magnet with a High Energy Barrier.

Fluoride-Bridged {Gd-III M-3(III) (2)} ( M= Cr, Fe, Ga) Molecular Magnetic Refrigerants**.

A symmetric, triply interlaced 3-D anionic MOF that exhibits both magnetic order and SMM behaviour.

Spin-1/2 Quantum Antiferromagnet on a Three-Dimensional Honeycomb Lattice Formed by a New Organic Biradical F4BIPBNN.

Stability of skyrmion textures and the role of thermal fluctuations in cubic helimagnets: A new intermediate phase at low temperature.

Identifying early pathogenic events during vascular calcification in uremic rats.

Exploring through-bond and through-space magnetic communication in 1,3,2-dithiazolyl radical complexes.

Structural Insights into the Two-Step Spin-Crossover Compound Fe(3,4-dimethyl-pyridine)(2)[Ag(CN)(2)](2).

Tetra-n-butylammonium orotate monohydrate: knowleage-based comparison of the results of accurate and lower-resolution analyses and a non-routine disorder refinement.

Polymorphism of the dinuclear Co-III-Schiff base complex [Co-2(o-van-en)(3)]center dot 4CH(3)CN (o-van-en is a 96 salen-type ligand).

Real-Time Intracellular Temperature Imaging Using Lanthanide Bearing Polymeric Micelles.

What is a crystal to the new chemical crystallographer, after that first, automated structure analysis?.

An Investigation of Halogen Bonding as a Structure-Directing Interaction in Dithiadiazolyl Radicals.

A decanuclear [(Dy6Zn4II)-Zn-III] cluster: a {Zn-4(II)} rectangle surrounding an octahedral {Dy-6(III)}.

Experimental Techniques

Typical experimental techniques employed frequently in these investigations

Neutron Scattering Techniques

Magnetometry

Thermal Properties

Synchrotron Techniques