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Issue 10, 2016
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Ferromagnetism in polynuclear systems based on non-linear [MnII2MnIII] building blocks

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Abstract

The design of new polynuclear transition metal complexes showing large total spin values through parallel alignment of the spins is an important challenge due to the scarcity of bridging ligands that provide ferromagnetic coupling. Herein, we report two new complexes, a [MnII4MnIII2] system containing two non-linear [MnII2MnIII] units and a 1D chain system with [MnII2MnIII] units that are assembled through dicyanamide bridging ligands coordinated to one of the terminal MnII centers. In both cases, the main exchange interaction is between MnII⋯MnIII, showing a relatively strong ferromagnetic coupling. Density functional theory calculations corroborate such ferromagnetic interactions and also provide one magnetostructural correlation, showing that larger MnII–O–MnIII angles enhance the strength of the ferromagnetic coupling. Thus, the non-linear [MnII2MnIII] units present in these two complexes are specially suited because of their larger MnII–O–MnIII angles compared to similar previously reported systems containing a linear [MnII2MnIII] unit.

Introduction to the international collaboration

The collaboration between Dr Wu's and Professor Ruiz's groups performs research on the synthetic chemistry of transition metal complexes with magnetic properties (Jilin University) and utilizes computational tools (University of Barcelona) to gain further insight into the nature of the physical properties of these systems. In this study, the interaction between our groups focused on the study of polynuclear systems containing an [MnII2MnIII] motif displaying ferromagnetic couplings. Such exchange pathways are needed to reach a large total spin value, which is one of the requirements to design single-molecule magnets. Thus, the synthesis of polynuclear complexes by Wu's group and subsequent density functional theory (DFT) calculations by the Ruiz group were performed in order to determine all the exchange interaction constants, corroborating the experimental data and provide further insight into the magnetic behavior of these systems. Previous collaborations between our groups included a similar approach for the study of [Mn10] cluster systems also showing ferromagnetic behavior due to MnII–MnIII interactions.

Graphical abstract: Ferromagnetism in polynuclear systems based on non-linear [MnII2MnIII] building blocks

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Supplementary files

Publication details

The article was received on 18 Jun 2016, accepted on 01 Aug 2016 and first published on 09 Aug 2016


Article type: Research Article
DOI: 10.1039/C6QI00189K
Citation: Inorg. Chem. Front., 2016,3, 1272-1279

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    Ferromagnetism in polynuclear systems based on non-linear [MnII2MnIII] building blocks

    J. Cirera, Y. Jiang, L. Qin, Y. Zheng, G. Li, G. Wu and E. Ruiz, Inorg. Chem. Front., 2016, 3, 1272
    DOI: 10.1039/C6QI00189K

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