A hexadecanuclear isobutyrate nanocluster with a {CoIII2CoII14} core
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Proprietăţile şi structura sistemelor moleculare (144)
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STATI, Dumitru; KRAVTSOV, Viktor; KRAMER, Karl W; AFFRONTE, M.; DECURTINS, Silvio; LIU, Shixia; BACAL, Svetlana. A hexadecanuclear isobutyrate nanocluster with a {CoIII2CoII14} core. In: Materials Science and Condensed Matter Physics. Ediția a 9-a, 25-28 septembrie 2018, Chișinău. Chișinău, Republica Moldova: Institutul de Fizică Aplicată, 2018, p. 159.
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Materials Science and Condensed Matter Physics
Ediția a 9-a, 2018
Conferința "International Conference on Materials Science and Condensed Matter Physics"
Chișinău, Moldova, 25-28 septembrie 2018

A hexadecanuclear isobutyrate nanocluster with a {CoIII2CoII14} core


CZU: 539.2+546
Pag. 159-159

Stati Dumitru1, Kravtsov Viktor1, Kramer Karl W2, Affronte M.3, Decurtins Silvio2, Liu Shixia2, Bacal Svetlana1
 
1 Institute of Applied Physics,
2 University of Bern,
3 Università di Modena e Reggio Emilia, Modena
 
Disponibil în IBN: 5 februarie 2019


Rezumat

Nano-sized clusters have attracted great attention over past decades due to their great potentials on technological and industrial applications, especialy in emerging fields such as development of ―intelligent‖ multifunctional materials including magnetic sensors and future spintronic devices. These species are particularly atractive combining the fascinating and useful physical properties with structural peculiarities such as large size and intriguing architectures.  In continuation of our research on the development of 3d and 3d-4f nanoclusters [1-2] we herein report the synthesis, structural characterization and magnetic behavior of a novel hexadecanuclear mixed-valence alcohol supported {CoIII2CoII14} isobutyrate nanocluster, formulated as [Co16(μ3-OH)4(μ2-H2O)2(is)20(thme)2(Hthme)2(H2O)4]·MeCN·4(H2O) (1) with a size of ca 3.0 × 1.7 × 1.4 nm. Compound 1 has been prepared from the reaction of dinuclear Co(II) isobutyrate with 1,1,1-tris(hydroxymethyl)ethane ligand (H3thme) and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. Nanocluster 1 crystallizes in the monoclinic space group P21/c with a = 19.4844(5), b = 19.7970(6), c = 20.2908(10) Å, ß = 93.527(3)°, V = 7812.0(5) Å3, resides on the inversion center, thus having Ci molecular symmetry. The metal atoms in the {CoIII2CoII14} cluster core are bridged by four hydroxy groups, two bridging water molecules, two triply deprotonated (thme3-) and two doubly deprotonated (Hthme2-) ligands, and twenty isobutyrate residues (Figure 1). Four water molecules complete the coordination sphere of four Co ions. Each of coordinated water molecules forms intramolecular O-H…O hydrogen bonds with oxygen atoms of neighboring isobutyrate ligands. The core structure of 1 can be considered as an arrangement of two planar {Co7} rings with a central CoIII atom surrounded by six CoII atoms interconnected by two additional CoII atoms. Each Co atom in 1 is six-coordinated and adopts an octahedral O6 coordination environment with the shorter CoIII-O bond distances of 1.890 – 1.916 Å and the longer CoII-O bond distances of 2.009 – 2.129 Å. Two solvent water molecules are trapped deeply within the cluster due to O-H...O H-bonds and form O-H...N hydrogen bonds with the external solvent acetonitrile molecule. The magnetic properties of 1 have also been studied and will be discussed in terms of known structure.