Hexanuclear pivalate cluster with a {MnIII2MnII4(μ4-O)2} core
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DARII, Mariana, CROITOR, Lilia, BOUROSH, Pavlina, KRAVTSOV, Victor, BACA, Svetlana. Hexanuclear pivalate cluster with a {MnIII2MnII4(μ4-O)2} core. In: Materials Science and Condensed Matter Physics, Ed. 8-th Edition, 12-16 septembrie 2016, Chişinău. Chişinău: Institutul de Fizică Aplicată, 2016, Editia 8, p. 158. ISBN 978-9975-9787-1-2.
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Materials Science and Condensed Matter Physics
Editia 8, 2016
Conferința "International Conference on Materials Science and Condensed Matter Physics"
8-th Edition, Chişinău, Moldova, 12-16 septembrie 2016

Hexanuclear pivalate cluster with a {MnIII2MnII4(μ4-O)2} core


Pag. 158-158

Darii Mariana, Croitor Lilia, Bourosh Pavlina, Kravtsov Victor, Baca Svetlana
 
Institute of Applied Physics, Academy of Sciences of Moldova
 
Proiecte:
 
Disponibil în IBN: 30 iulie 2019


Rezumat

Hexanuclear manganese carboxylate [Mn6O2(piv)10(L)4] clusters (Hpiv = pivalic acid, L = neutral monodentate ligand) represent attractive candidates for the construction of cluster-based polymeric materials [1,2] due to possibility of modification with respect to size and solution properties by judicious choice of carboxylate and capping ligands, while the topology of the cluster skeleton remains invariant, the four capping ligands L in such clusters may be completely or partially replaced, thus [Mn6O2(piv)10] fragments might be viewed as tectonic building blocks with connectivity up to four. A new hexanuclear [MnIII2MnII4(μ4-O)2(piv)10(Hpiv)3(C2H5OH)]·(Hpiv) (1) cluster has been synthesized and structurally characterized by X-ray study. Compound 1 crystallizes in the centrosymmetric space group P-1: a = 13.518(2), b = 15.873(2), c = 25.479(4) Å, α = 73.161(13), β = 80.243(13), γ = 66.533(15)°. The cluster contains a {MnII4MnIII2O2}10+ core of two edge sharing Mn4 tetrahedra, with a μ4-O2-ion in the center of each tetrahedron. Peripheral ligation is provided by ten bridging pivalate monoanionic ligands (Fig.1). Four of them coordinate in a μ3mode and bridge three Mn centers whereas the other six each bridge two Mn centers in a μ2-mode. Within the core, the two central Mn centers are in the oxidation state +3, and the four terminal Mn atoms are in the lower oxidation state +2. All MnII/III ions in the {Mn6} unit are six-coordinated with a distorted octahedral O6 environment. Two central MnIII sites are bridged by two μ4-O atoms which, together with two O atoms from two carboxylates, define the equatorial plane; two additional η2-O atoms from μ3-carboxylate bridges occupy the axial positions. Four peripheral MnII sites adopt a similar coordination environment of four O atoms from carboxylate ligands in a common plane and trans-positioned μ4-O and oxygen atom of ethanol molecule (Mn4) or monodentate pivalic acid (Mn3, Mn5 and Mn6). The arrangement of the later is additionally stabilized by intramolecular O–H…O hydrogen bonds.