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Nouvelle publication de l’équipe CIEL : « Synthetic ability of dinuclear mesocates containing 1,3-bis(diazinecarboxamide)benzene bridging ligands to form complexes of increased nuclearity. Crystal structures, magnetic properties and theoretical studies. »

Maria A. Palacios, Jessica Morlieras, Juan Manuel Herrera, Antonio J. Mota, Euan K. Brechin, Smail Triki and Enrique Colacio

Dalton Trans., 2017,46, 10469-10483
DOI: 10.1039/C7DT02288C

Abstract :

Triple stranded NiII2-metallacyclic complexes Na2.5[Ni2(bpcb)3]·0.5OH·18.5H2O (1) and Na2[Ni2(bpzcb)3]·16H2O (2), and double stranded CuII2-metallacyclic complexes [Cu2(bpcb)2(H2O)2]·8H2O (3) and [Cu2(bpzcb)2(H2O)2]·4H2O (4) have been assembled from the tailored bisbidentate bridging ligands, 1,3-bis(pyrimidine-2-carboxamide)benzene (H2bpcb) and 1,3-bis(pyrazine-2-carboxamide)benzene (H2bpzcb), and the corresponding nitrate salts of the metal ions. Following the “complex as ligand” strategy, 1 can be assembled with either Ni2+, Co2+ ions or the [Mn(acen)Cl] complex to afford unique, neutral, bent trinuclear molecules [MIINiII2(bpcb)3xH2O (5 and 6) and the 2D honeycomb-like complex (PPh4){[Ni2(bpcb)3]2[Mn(acen)]3} (7), respectively. In these cases, the Ni2 units are linked to the corresponding metal ions through amidate oxygen atoms and the outward nitrogen atom of one of the pyrimidine rings of the bcpb ligand. The assembly of 2 with Ln3+ ions (Ln3+ = Tb, Gd) leads to one dimensional complexes of formula [{[Ni2(bpzcb)3]Tb(H2O)5}(CF3SO3)·THF·5H2O]n (8) and [{[Ni2(bpzcb)3]Ln(H2O)4(NO3)}·2THF·nH2O]n (9 and 10) (Ln3+ = Gd and Tb), where the dinuclear Ni2 units are joined to two Ln3+ ions exclusively through amidate oxygen atoms of two different ligands. The analyses of the magnetic data indicate that 1–4 exhibit intradinuclear ferromagnetic interactions between the metal ions through a spin polarisation mechanism, as supported by DFT calculations. Trinuclear complexes 5 and 6 show predominant antiferromagnetic coupling, which is a result of an antiferromagnetic interaction between one of the Ni2+ ions of the Ni2 unit and the M2+ ion through the pyrimidine bridging fragment that is stronger than the polarised ferromagnetic interaction between the Ni2+ ions through the bpcb ligand in the dinuclear [Ni2(bpcb)3]2− moiety. Complex 7 shows a dominant antiferromagnetic interaction between the Ni2+ and Mn2+, whereas the Ni2Ln (Ln3+ = Gd, Tb) chain complexes present ferromagnetic interactions inside the Ni2 mesocate unit as well as between the Ni2+ ions of the Ni2 unit and the Ln3+ ions. The magnetic exchange interactions in these new materials have been experimentally analysed and supported by theoretical DFT studies.