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|Type:||Artigo de periódico|
|Title:||1-Methyl-2-Pyrrolidone: From Exfoliating Solvent to a Paramagnetic Ligand|
|Abstract:||When 1-methyl-2-pyrrolidone molecule (1m2p) interacts with the T[Ni(CN)(4)] layer, its carbonyl g bond homolytically disrupts and forms a coordination bond at the axial positions for the metal T, and hybrid inorganic-organic solids of formula unit T(L)(2)[Ni(CN)(4)], with T = Mn, Co, Ni, are obtained. The formed solids crystallize with a monoclinic unit cell in the C2/m space group where the metal T is found with octahedral coordination to four N ends of CN groups from a given layer and to two oxygen atoms from the organic ligands, while the inner metal (Ni) preserves its square planar coordination. In the interlayer region, the organic molecules achieve unusual planarity and are stacked through dipole-dipole interactions in a head-to-tail configuration to form a chain of molecular pillars. From such interactions, 3D pillared hybrid solids result. Upon the charge donation to the metal by oxygen atom from 1m2p, the latter becomes an organic radical whose SOMO frontier orbital has a strong pi character, associated with an essentially planar structure. The unpaired electron is delocalized between neighboring C and N atoms at the ligand ring plane, and it is featured by an outstanding broad absorption band in the near-IR region. For Ni, the metal of highest polarizing power within the considered series, the existence of pi overlapping interaction between organic ligand molecules leads to ferromagnetic ordering at low temperature, with T-C = 10.07 K. For Mn and Co, related to the lower metal electron-withdrawing ability, the materials maintain the weak antiferromagnetic character resulting from the interaction between T metals in the layer -T-NC Ni-C N-T-chains.|
|Editor:||Amer Chemical Soc|
|Appears in Collections:||Artigos e Materiais de Revistas Científicas - Unicamp|
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