English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/75401
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:

Thiodiacetate-manganese chemistry with N ligands: Unique control of the supramolecular arrangement over the metal coordination mode

AuthorsGrirrane, Abdessamad; Pastor, Antonio; Galindo, Agustín; Álvarez, Eleuterio ; Mealli, Carlo; Ienco, Andrea; Orlandini, Annabella, Rosa, Patrick; Caneschi, Andrea; Barra, Anne-Laure; Fernández Sanz, Javier
Issue Date2011
PublisherJohn Wiley & Sons
CitationChemistry - A European Journal 17: 10600- 10617 (2011)
AbstractCompounds based on the Mn-tda unit (tda=S(CH2COO) 2 -2) and N co-ligands have been analyzed in terms of structural, spectroscopic, magnetic properties and DFT calculations. The precursors [Mn(tda)(H2O)]n (1) and [Mn(tda)(H 2O)3]·H2O (2) have been characterized by powder and X-ray diffraction, respectively. Their derivatives with bipyridyl-type ligands have formulas [Mn(tda)(bipy)]n (3), [{Mn(N-N)}2(μ-H2O)(μ-tda)2]n (N-N=4,4′-Me2bipy (4), 5,5′-Me2bipy, (5)) and [Mn(tda){(MeO)2bipy}·2 H2O]n (6). Depending on the presence/position of substituents at bipy, the supramolecular arrangement can affect the metal coordination type. While all the complexes consist of 1D coordination polymers, only 3 has a copper-acetate core with local trigonal prismatic metal coordination. The presence of substituents in 4-6, together with water co-ligands, reduces the supramolecular interactions and typical octahedral MnII ions are observed. The unicity of 3 is also supported by magnetic studies and by DFT calculations, which confirm that the unusual Mn coordination is a consequence of extended noncovalent interactions (π-π stacking) between bipy ligands. Moreover, 3 is an example of broken paradigm for supramolecular chemistry. In fact, the desired stereochemical properties are achieved by using rigid metal building blocks, whereas in 3 the accumulation of weak noncovalent interactions controls the metal geometry. Other N co-ligands have also been reacted with 1 to give the compounds [Mn(tda)(phen)]2·6 H2O (7) (phen=1,10- phenanthroline), [Mn(tda)(terpy)]n (8) (terpy=2,2′:6, 2′′-terpyridine), [Mn(tda)(pyterpy)]n (9) (pyterpy=4′-(4-pyridyl)-2,2′:6,2′′-terpyridine), [Mn(tda)(tpt)(H2O)]·2 H2O (10) and [Mn(tda)(tpt)(H2O)]2·2 H2O (11) (tpt=2,4,6-tris(2-pyridyl)-1,3,5-triazine). Their identified mono-, bi-or polynuclear structures clearly indicate that hydrogen bonding is variously competitive with π-π stacking. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Identifiersdoi: 10.1002/chem.201100988
issn: 0947-6539
Appears in Collections:(IIQ) Artículos
Files in This Item:
File Description SizeFormat 
accesoRestringido.pdf15,38 kBAdobe PDFThumbnail
Show full item record
Review this work

Related articles:

WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.