Magnetism; Actinides; Uranium; Pentavalent Uranium; Single Molecule Magnets; Coordination chemistry; Supramolecular Chemistry
Barluzzi Luciano, Chatelain Lucile, Fadaei-Tirani Farzaneh, Zivkovic Ivica, Mazzanti Marinella (2019), Facile N-functionalization and strong magnetic communication in a diuranium( v ) bis-nitride complex, in Chemical Science
, 10(12), 3543-3555.
Falcone Marta, Barluzzi Luciano, Andrez Julie, Fadaei Tirani Farzaneh, Zivkovic Ivica, Fabrizio Alberto, Corminboeuf Clemence, Severin Kay, Mazzanti Marinella (2019), The role of bridging ligands in dinitrogen reduction and functionalization by uranium multimetallic complexes, in Nature Chemistry
, 11(2), 154-160.
Faizova Radmila, White Sarah, Scopelliti Rosario, Mazzanti Marinella (2018), The effect of iron binding on uranyl( v ) stability, in Chemical Science
, 9(38), 7520-7527.
Falcone Marta, Chatelain Lucile, Scopelliti Rosario, Živković Ivica, Mazzanti Marinella (2017), Nitrogen reduction and functionalization by a multimetallic uranium nitride complex, in Nature
, 547(7663), 332-335.
Chatelain Lucile, Tuna Floriana, Pécaut Jacques, Mazzanti Marinella (2017), Synthesis and SMM behaviour of trinuclear versus dinuclear 3d–5f uranyl( v )–cobalt( ii ) cation–cation complexes, in Dalton Transactions
, 46(17), 5498-5502.
The overall goal of this project is to find new molecular systems that can store magnetic information at reasonable temperature. Uranium compounds are attractive candidates for the development of new molecules displaying slow magnetic relaxation of a purely molecular origin (i.e. single-molecule magnets, or SMMs). Compared to d-block or f-block elements, the high magnetic anisotropy of the uranium ion over a range of oxidation states, combined with its ability to engage in strong magnetic exchange interactions with other metal centres, makes it particularly promising for the development of SMMs possessing barriers to spin reversal high enough to observe hysteresis at reasonable temperatures-a crucial prerequisite for the application of SMMs in high density data storage, quantum computing and spintronics devices. In this project we propose to design original uranium based molecular and supramolecular systems for the development of molecular magnets with higher spin-inversion barriers and higher hysteresis temperatures than currently obtained. This will be achieved trough an interdisciplinary approach combining the rational synthesis of new uranium compounds and the development of models for the analysis of the magnetic properties. We envisage to explore two original strategies. In the first strategy we will take advantage of the single ion anisotropy of the UO2+ cation and of the ability of this cation to bind other metal cations trough the oxo group for the development of poly-homometallic and poly-heterometallic complexes with single molecule magnet properties. Subtle ligand tuning and carefully chosen synthetic methods will be developed to prevent disproportionation of the UO2+ cation and to promote self-assembly of discrete compounds. High spin-inversion barriers and hysteresis temperatures should result from associating the anisotropic UO2+ cation and d-block and f-block metal cations with a high total spin. Moreover, the simple 5f1 electronic structure is an excellent starting point for the development of magnetic models, an essential step for understanding the structure-properties relation.In the second approach polymetallic complexes of U(III) will be prepared with the goal of promoting ferromagnetic coupling between the two U(III) ions leading to SMM behavior at higher temperatures. In both strategies, the study of the magnetic properties of the new compounds synthesized and their quantitative analysis will be essential for the understanding of the spin exchange mechanisms and of the parameters affecting SMM behavior, which in turn will provide input for the synthesis of compounds with higher spin-inversion barriers and showing magnetic hysteresis at higher temperatures, a crucial step for applications such as high density information storage devices, spintronics or quantum computing.