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      Coordination Clusters of 3d-Metals That Behave as Single-Molecule Magnets (SMMs): Synthetic Routes and Strategies

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          Abstract

          The area of 3d-metal coordination clusters that behave as Single-Molecule Magnets (SMMs) is now quite mature within the interdisciplinary field of Molecular Magnetism. This area has created a renaissance in Inorganic Chemistry. From the synthetic Inorganic Chemistry viewpoint, the early years of “try and see” exercises (1993–2000) have been followed by the development of strategies and strict approaches. Our review will first summarize the early synthetic efforts and routes for the preparation of polynuclear 3d-metal SMMs, and it will be then concentrated on the description of the existing strategies. The former involve the combination of appropriate 3d-metal-containing starting materials (simple salts with inorganic anions, metal cardoxylates, and pre-formed carboxylate clusters, metal phosphonates) and one or two primary organic ligands; the importance of the end-on azido group as a ferromagnetic coupler in 3d-metal SMM chemistry will be discussed. The utility of comproportionation reactions and the reductive aggregation route for the construction of manganese SMMs will also be described. Most of the existing strategies for the synthesis of SMMs concern manganese. These involve substitution of carboxylate ligands in pre-formed SMMs by other carboxylate or non-carboxylate groups, reduction procedures for the { Mn 8 III Mn 4 IV } SMMs, spin “tweaking,” “switching on” SMM properties upon conversion of low-spin clusters into high-spin ones, ground-state spin switching and enhancing SMM properties via targeted structural distortions, the use of radical bridging ligands and supramolecular approaches. A very useful strategy is also the “switching on” of SMM behavior through replacement of bridging hydroxide groups by end-on azido or isocyanato ligands in clusters. Selected examples will be mentioned and critically discussed. Particular emphasis will be given on the criteria for the choice of ligands.

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          Molecular spintronics using single-molecule magnets.

          A revolution in electronics is in view, with the contemporary evolution of the two novel disciplines of spintronics and molecular electronics. A fundamental link between these two fields can be established using molecular magnetic materials and, in particular, single-molecule magnets. Here, we review the first progress in the resulting field, molecular spintronics, which will enable the manipulation of spin and charges in electronic devices containing one or more molecules. We discuss the advantages over more conventional materials, and the potential applications in information storage and processing. We also outline current challenges in the field, and propose convenient schemes to overcome them.
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            Macroscopic quantum tunnelling of magnetization in a single crystal of nanomagnets

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              Macroscopic Measurement of Resonant Magnetization Tunneling in High-Spin Molecules

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                Author and article information

                Contributors
                Journal
                Front Chem
                Front Chem
                Front. Chem.
                Frontiers in Chemistry
                Frontiers Media S.A.
                2296-2646
                09 October 2018
                2018
                : 6
                : 461
                Affiliations
                Department of Chemistry, University of Patras , Patras, Greece
                Author notes

                Edited by: Matilde Fondo, Universidade de Santiago de Compostela, Spain

                Reviewed by: Ramon Vicente, University of Barcelona, Spain; Giannis Papaefstathiou, National and Kapodistrian University of Athens, Greece

                *Correspondence: Spyros P. Perlepes perlepes@ 123456patreas.upatras.gr

                This article was submitted to Inorganic Chemistry, a section of the journal Frontiers in Chemistry

                Article
                10.3389/fchem.2018.00461
                6190736
                b54f4ef0-d8f2-4e55-908f-073e52bfd8d0
                Copyright © 2018 Maniaki, Pilichos and Perlepes.

                This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

                History
                : 03 July 2018
                : 14 September 2018
                Page count
                Figures: 14, Tables: 0, Equations: 88, References: 133, Pages: 28, Words: 20737
                Categories
                Chemistry
                Review

                3d-metal single-molecule magnets,synthetic routes,synthetic strategies,coordination clusters,magnetic properties,reactivity studies,manganese single-molecule magnets,ligand design

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