The double stranded CuII2-metallacyclic complex of formula [Cu2(mbpb)2]·2H2O (1) and the triple stranded NiII2-metallacyclic complexes of formula [Ni2(Hmbpb)3]PF6·21H2O (2), [Co(H2O)6][Ni2(mbpb)3] THF·10H2O (3) and Ag2(H2O)[Ni 2(mbpb)3]·11H2O (4) (where H 2mbpb is the bisbidentate dinucleating bridging ligand 1,3-bis(pyridine-2-carboxamide) benzene) have been synthesised and characterised by single-crystal X-ray diffraction. Within the dinuclear molecules, metal ions are bridged by either fully or semideprotonated bisbidentate ligands, which are coordinated through the pyridine and amidato nitrogen donor atoms. In complex 4 the triple stranded dinuclear Ni2 units are connected to the Ag + cations through O-amidato bridges and Ag-π(benzene) interactions to afford a 1D bimetallic chain. Cu2 (1) and Ni 2 (2-4) complexes exhibit ferromagnetic coupling between the metal ions through the bridging ligand with JCu-Cu = 21.1 cm-1 and JNi-Ni in the range of 2.9-3.6 cm-1, respectively. Amongst copper(ii) dinuclear complexes bearing m-phenylenediamidato bridges, complex 1 exhibits the stronger ferromagnetic exchange coupling reported so far. DFT calculations firstly confirm that the spin polarisation mechanism is responsible for the ferromagnetic coupling, and secondly allows us to predict stronger ferromagnetic couplings in CuII2 complexes with larger tetrahedral distortions of the CuN4 coordination environment. © 2009 The Royal Society of Chemistry.

Enhanced ferromagnetic interaction in metallacyclic complexes incorporating m-phenylenediamidato bridges / M. A. Palacios, A. Rodríguez-Diéguez, A. Sironi, J.M. Herrera, A.J. Mota, J. Cano, E. Colacio. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - :40(2009), pp. 8538-8547.

Enhanced ferromagnetic interaction in metallacyclic complexes incorporating m-phenylenediamidato bridges

A. Sironi;
2009

Abstract

The double stranded CuII2-metallacyclic complex of formula [Cu2(mbpb)2]·2H2O (1) and the triple stranded NiII2-metallacyclic complexes of formula [Ni2(Hmbpb)3]PF6·21H2O (2), [Co(H2O)6][Ni2(mbpb)3] THF·10H2O (3) and Ag2(H2O)[Ni 2(mbpb)3]·11H2O (4) (where H 2mbpb is the bisbidentate dinucleating bridging ligand 1,3-bis(pyridine-2-carboxamide) benzene) have been synthesised and characterised by single-crystal X-ray diffraction. Within the dinuclear molecules, metal ions are bridged by either fully or semideprotonated bisbidentate ligands, which are coordinated through the pyridine and amidato nitrogen donor atoms. In complex 4 the triple stranded dinuclear Ni2 units are connected to the Ag + cations through O-amidato bridges and Ag-π(benzene) interactions to afford a 1D bimetallic chain. Cu2 (1) and Ni 2 (2-4) complexes exhibit ferromagnetic coupling between the metal ions through the bridging ligand with JCu-Cu = 21.1 cm-1 and JNi-Ni in the range of 2.9-3.6 cm-1, respectively. Amongst copper(ii) dinuclear complexes bearing m-phenylenediamidato bridges, complex 1 exhibits the stronger ferromagnetic exchange coupling reported so far. DFT calculations firstly confirm that the spin polarisation mechanism is responsible for the ferromagnetic coupling, and secondly allows us to predict stronger ferromagnetic couplings in CuII2 complexes with larger tetrahedral distortions of the CuN4 coordination environment. © 2009 The Royal Society of Chemistry.
Settore CHIM/03 - Chimica Generale e Inorganica
Article (author)
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/179660
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 28
  • ???jsp.display-item.citation.isi??? 26
social impact