Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoIII2MnII2MnIV2 cluster sustained by a multidentate Schiff base ligand
| Autor: | Oleh Stetsiuk, Vladimir N. Kokozay, Miguel Julve, Joan Cano, Benoit Fleury, Narcis Avarvari, Abdelkrim El-Ghayoury, Svitlana R. Petrusenko, Francesc Lloret, Valentyn Synytsia |
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| Přispěvatelé: | MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia Molecular (ICMol), Universitat de València (UV), Departament de Química Inorgànica,Instituto de Ciencia Molecular (ICMOL), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2019 |
| Předmět: |
Denticity
Schiff base Valence (chemistry) Materials science Spin states 010405 organic chemistry Metal ions in aqueous solution 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Oxidation state [CHIM]Chemical Sciences Antiferromagnetism [CHIM.COOR]Chemical Sciences/Coordination chemistry ComputingMilieux_MISCELLANEOUS Monoclinic crystal system |
| Zdroj: | Dalton Transactions Dalton Transactions, Royal Society of Chemistry, 2019, 48 (31), pp.11862-11871. ⟨10.1039/c9dt02503k⟩ |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/c9dt02503k |
| Popis: | The successful utilization of the “direct synthesis” approach yielded the unprecedented hexanuclear complex of formula [Co2MnII2MnIV2(L1)4Cl2(μ3-O)2(dmf)4]·2dmf (1) (H3L is the Schiff base derived from the condensation of salicylaldehyde and 3-aminopropane-1,2-diol). Single crystal X-ray analysis revealed that 1 crystallizes in the monoclinic system P21/c and it contains a rare mixed-valence {CoIII2MnII2MnIV2(μ2-O)8(μ3-O)2} core where all metal ions are linked through the phenolato and alkoxo groups of the L3− ligand. Besides the charge balance resulting from the X-ray structure, the oxidation state of the metal ions has been confirmed by XPS spectroscopy. Cryomagnetic studies indicate the coexistence of ferro- (MnIV–MnII, J2 = +1.10(3) cm−1, J3 = +2.19(3) cm−1; MnII–MnII, j = +0.283(3) cm−1) and antiferromagnetic interactions (MnIV–MnIV, J1 = −17.31(4) cm−1), with the six-coordinate CoIII ions being diamagnetic. DFT type calculations were carried out to substantiate these values. The energy diagram for the different spin states using the best-fit parameters shows the occurrence of six low-lying spin states (S = 0–5) which are close in energy but clearly separated from the remaining ones, with the ground spin state being S = 5. Complex 1 is found to be the first example where weak ferromagnetic exchange between MnII ions through the long –O–MnIV–O– pathway takes place. |
| Databáze: | OpenAIRE |
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