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Magnetochemistry 2016, 2(3), 30; doi:10.3390/magnetochemistry2030030

A Ni11 Coordination Cluster from the Use of the Di-2-Pyridyl Ketone/Acetate Ligand Combination: Synthetic, Structural and Magnetic Studies

1
Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus
2
Chemistry Department, Arts/Science Building, National University of Ireland Galway, University Road, Galway, Ireland
3
Department of Chemistry, University of Patras, 265 04 Patras, Greece
4
Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 10 Aghia Paraskevi Attikis, Greece
5
Departament de Quimica Inorganica and Institute of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona, Diagonal 645, 08028 Barcelona, Spain
6
Institute of Chemical Engineering Sciences, Foundation for Research and Technology-Hellas (FORTH/ICE-HT), Platani, P.O. Box 1414, 265 04 Patras, Greece
*
Authors to whom correspondence should be addressed.
Academic Editor: Núria Aliaga-Alcalde
Received: 21 May 2016 / Revised: 15 July 2016 / Accepted: 21 July 2016 / Published: 2 August 2016
(This article belongs to the Special Issue Magnetism Regarding Coordination Clusters, Polymers and MOFs)
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Abstract

The combined use of di-2-pyridyl ketone, (py)2CO, and acetates (MeCO2) in nickel(II) chemistry in H2O-MeCN under basic conditions (Et3N) afforded the coordination cluster [Ni11(OH)6(O2CMe)12{(py)2C(OH)(O)}4(H2O)2] (1) in 80% yield, where (py)2C(OH)(O) is the monoanion of the gem-diol form of (py)2CO. The complex contains a novel core topology. The core of 1 comprises a central non-linear {Ni32-OH)4}2+ subunit which is connected to two cubane {Ni4(OH)(μ3-OR)23-OR′)}4+ subunits [RO = (py)2C(OH)(O) and R′O = MeCO2] via the OH groups of the former which become μ3. The linkage of the Ni3 subunit to each Ni4 subunit is completed by two η112 and one η134 MeCO2 groups. Peripheral ligation is provided by two terminal monodentate MeCO2 and two terminal aqua ligands. The (py)2C(OH)(O) ligands adopt the η1133 coordination mode. From the twelve MeCO2 ligands, two are η1, two η134 and eight adopt the syn, syn η112 coordination mode; four of the latter bridge NiII centers at opposite faces of the cubane subunits. Complex 1 is the largest nickel(II)/(py)2CO-based ligand coordination cluster discovered to date and has an extremely rare nuclearity (Ni11) in the cluster chemistry of nickel(II). Variable-temperature, solid state dc susceptibility, and variable-field magnetization studies at low temperatures were carried out on complex 1. The study of the data reveals an S = 3 ground state, which has been well rationalized in terms of known magnetostructural correlations and the structural features of 1. An attempt has also been made to interpret the magnetic properties of the undecanuclear cluster in a quantitative manner using four exchange interaction parameters and the obtained J values are discussed. The role of H2O in the solvent medium that led to 1, and the high nickel(II) and acetate to di-2-pyridyl ketone reaction ratio employed for its preparation, on the nuclearity and identity of the cluster are critically analyzed. View Full-Text
Keywords: ancillary carboxylate ligands; coordination clusters; di-2-pyridyl ketone-based ligands; nickel(II); magnetic properties; undecanuclearity in nickel(II) chemistry ancillary carboxylate ligands; coordination clusters; di-2-pyridyl ketone-based ligands; nickel(II); magnetic properties; undecanuclearity in nickel(II) chemistry
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G. Efthymiou, C.; Mylonas-Margaritis, I.; P. Raptopoulou, C.; Psycharis, V.; Escuer, A.; Papatriantafyllopoulou, C.; P. Perlepes, S. A Ni11 Coordination Cluster from the Use of the Di-2-Pyridyl Ketone/Acetate Ligand Combination: Synthetic, Structural and Magnetic Studies. Magnetochemistry 2016, 2, 30.

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