Synthesis and structure of molecular magnets

Molecular Materials

The study of molecular materials extends the long-established field of materials development into the realm of molecular solids. The basic building blocks of molecular solids are covalently bonded fragments in either discrete form (also known as zero-D) with only non-covalent interactions with their surroundings, or in covalently bound 1D, 2D or 3D polymeric assemblies, which may also establish non-covalent interactions with their surroundings. 

Molecular materials have attractive potential advantages that include light weight, low cost, low density, flexibility and tunability, among others. The most important fundamental advantage is that all of the properties of molecular materials can in principle be modified through adjustments to the chemical composition of the basic building blocks of the material. 

This group prepares and studies new molecular solids, with a focus on aspects that may lead to useful molecular-materials applications. Within a more general study of preparation, characterization and internal structure, we seek out molecular solids that can undergo non-destructive transformations, as a means of preparing solids that cannot be prepared any other way and in order to add a further dimension — switchability — to the properties of the solid. 

Non-covalent forces can play an important role — advantageous or adverse — with respect to the plasticity needed for non-destructive transformations.  

We have discovered a series of novel behaviors of molecular solids in a diversity of areas. Based on what we have observed to date, we are confident that an even broader array of such behaviors awaits discovery. All of the following take place in molecular crystals.

Contributions in the field of molecular magnetism


Exceptionally slow magnetic relaxation in cobalt(II) benzoate trihydrate
Dalton Trans., 47, 15523-15529, 2018.

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A Tetragonal Two-Dimensional Array of Single-Molecule Magnets with Modulable Collective Behavior.
Chem. Eur. J. 17, 2818-2822, 2011.

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Symmetric, triply interlaced 3-D anionic MOF that exhibits both magnetic order and SMM behavior.
Dalton Trans., 45, 16764-16768, 2016.

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New preparation, first structure analysis and magnetism of the long-known nickel benzoate trihydrate: A rigorously linear Ni∙∙∙Ni∙∙∙Ni polymer and its parallels to the active site of urease.
Eur. J. Inorg. Chem. 2016, 928-934, 2016. .

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Slow Magnetic Relaxations in a Ladder-Type Dy(III) Complex and its Dinuclear Isomer.
Dalton Trans., 46, 5344-5351, 2017.

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Ce, Gd, Dy

Slow magnetic relaxation in Ni-Ln (Ln = Ce, Gd, Dy) dinuclear complexes
Dalton Trans., 48, 13943-13952, 2019.

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Other areas of interest

Phase Transitions

Tunable molecular shape in a molecule coupled with a second-order phase transition in the Crystalline State
J. Am. Chem. Soc. 121, 2808-2819, 1999.

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Reactions in Crystals

Reversible Single-Crystal-to-Single-Crystal Crosslinking of a Ribbon of Cobalt Citrate Cubanes to Form a 2D Net.
J. Am. Chem. Soc. 130, 2932-2933, 2008.

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Proton conduction

Proton cascade in a molecular solid: H/D exchange on mobile and immobile water.
Angewandte Chemie Int. Ed. 52, 13463-13467, 2013.

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New Geometries

A Route to Small Clusters: A Twisted Half-Hexagram-Shaped M4(OH)4 Cluster and Its Capacity for Hosting Closed-Shell Metals.
Chem. Comm. 53, 13121-13124, 2017.

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Last projects

Preparación y estudio de Materiales Magnéticos Multifuncionales de carácter Molecular

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

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

MAT-2015-68200-C2-1-P (M4c2m) Ministerio de Economía y Competitividad (2016-2018)

Magnetismo, conducción protónica y transformaciones de monocristal a monocristal en sólidos moleculares de compuestos de coordinación 3D/4D con ligandos polifuncionales.

PGC2018-093451-B-I00 Ministerio de Ciencia, Innovacion y Universidades (2019-2021)

Recent publications

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

M. Ohkuma, M. Mito, M. Pardo, Y. Kousaka, S. Iwasaki, K. Ohishi, J. Akimitsu, K. Inoue, V. Laliena, J. Campo.

Magnonic Goos-Hänchen effect induced by one dimensional solitons

Victor Laliena, Javier Campo

Creation of single chiral soliton states in monoaxial helimagnets

S. A. Osorio, V. Laliena, J. Campo, and S. Bustingorry

Large magnetocaloric effect in EuGd2O4 and EuDy2O4

E.Palacios, R.Sáez-Puche, J.Romero, Y.Doi, Y.Hinatsu, M.Evangelisti

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

Daniel Joven-Sancho, Miguel Baya, Larry R. Falvello, Antonio Martín, Jesús Orduna and Babil Menjón*

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

Miguel Angel Vicente Alvarez; Victor Laliena; Florencia Malamud; Javier Campo; Javier Santisteban

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

Yuanyu Gu; Nuno J. O. Silva; Marie Yoshikiyo; Asuka Namai; Rafael Pinñol; Guillaume Maurin-Pasturel; Yuwen Cui; Shin-ichi Ohkoshi; Angel Millan; Abelardo Martinez

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

Thomais G. Tziotzi; Marco Coletta; Mark Gray; Cameron L. Campbell; Scott J. Dalgarno; Giulia Lorusso; Marco Evangelisti; Euan K. Brechin; Constantinos J. Milios;

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

Arevalo, Rebeca; López, Ramón; Falvello, Larry R.; Riera, Lucía; Perez, Julio

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

Černák, Juraj; Harčarová, Katarína; Falvello, Larry R.; Dlháň, Ľubor; Boča, Roman

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

Anna Vráblová, Milagros Tomás, Ján Titiš, Juraj Černák and Larry R. Falvello.

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

J. Lohr, A. L. Larralde, J. Curiale, R. Sanchez, J. Campo, G. J. Cuello, D. Sheptyakov, L. Keller, M. Kenzelmann, G. Aurelio

Dynamics of chiral solitons driven by polarized currents in monoaxial helimagnets

Laliena, Victor; Bustingorry, Sebastian; Campo Javier;

Design and optimization of a magnet for magnetocaloric refrigeration.

Francisco Beltran-Lopez, Jesus; Palacios, Elias; Velazquez, David; Burriel, Ramon

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

Hernandez-Rodriguez, Miguel A.; Brites, Carlos D. S.; Antorrena, Guillermo; Pinol, Rafael; Cases, Rafael; Perez-Garcia, Lluisa; Rodrigues, Mafalda; Plaza, Jose Antonio; Torras, Nuria; Diez, Isabel; Millan, Angel; Carlos, Luis D.

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

Rodriguez-Velamazan, J. Alberto; Fabelo, Oscar; Campo, Javier; Rodriguez-Carvajal, Juan; Qureshi, Navid; Chapon, Laurent C.

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

Evangelisti, M; Candini, A; Ghirri, A; Affronte, M; Piligkos, S; Brechin, EK; McInnes, EJL

Thermometry at the nanoscale.

Brites, Carlos D. S.; Lima, Patricia P.; Silva, Nuno J. O.; Millan, Angel; Amaral, Vitor S.; Palacio, Fernando; Carlos, Luis D.

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

Oyarzabal, Itziar; Ruiz, Jose; Manuel Seco, Jose; Evangelisti, Marco; Camon, Agustin; Ruiz, Eliseo; Aravena, Daniel; Colacio, Enrique

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

Pedersen, Kasper S.; Lorusso, Giulia; Morales, Juan Jose; Weyhermueller, Thomas; Piligkos, Stergios; Singh, Saurabh Kumar; Larsen, Dennis; Schau-Magnussen, Magnus; Rajaraman, Gopalan; Evangelisti, Marco; Bendix, Jesper

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

Campo, J.; Falvello, L. R.; Forcen-Vazquez, E.; Saenz de Pipaon, C.; Palacio, F.; Tomas, M.

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

Amaya, Naoki; Ono, Toshio; Oku, Yuta; Yamaguchi, Hironori; Matsuo, Akira; Kindo, Koichi; Nojiri, Hiroyuki; Palacio, Fernando; Campo, Javier; Hosokoshi, Yuko

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

Laliena, Victor; Campo, Javier

Identifying early pathogenic events during vascular calcification in uremic rats.

Hortells, Luis; Sosa, Cecilia; Guillen, Natalia; Lucea, Susana; Millan, Angel; Sorribas, Victor

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

Leckie, Dominique; Stephaniuk, Nadia T.; Arauzo, Ana; Campo, Javier; Rawson, Jeremy M.

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

Rodriguez-Velamazan, Jose Alberto; Kitase, Kosuke; Palacios, Elias; Castro, Miguel; Fernandez-Blanco, Angel; Burriel, Ramon; Kitazawa, Takafumi

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

Ara, Irene; Basdouri, Zeineb; Falvello, Larry R.; Graia, Mohsen; Guerra, Pablo; Tomas, Milagros

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).

Vrablova, Anna; Cernak, Juraj; Falvello, Larry R.; Tomas, Milagros

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

Pinol, Rafael; Zeler, Justyna; Brites, Carlos D. S.; Gu, Yuanyu; Tellez, Pedro; Carneiro Neto, Albano N.; da Silva, Thiago E.; Moreno-Loshuertos, Raquel; Fernandez-Silva, Patricio; Isabel Gallego, Ana; Martinez-Lostao, Luis; Martinez, Abelardo; Carlos, Luis D.; Millan, Angel

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

Falvello, Larry R.

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

Nascimento, Mitchell A.; Heyer, Elodie; Less, Robert J.; Pask, Christopher M.; Arauzo, Ana; Campo, Javier; Rawson, Jeremy M.

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

Stavgianoudaki, Nikoleta; Siczek, Milosz; Lis, Tadeusz; Lorusso, Giulia; Evangelisti, Marco; Milios, Constantinos J.