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From Mesocates to Helicates: Structural, Magnetic and Chiro-Optical Studies on Nickel(II) Supramolecular Assemblies
Júlia Mayans1, Mercè Font-Bardia2, Lorenzo Di Bari3
1Departament de Química Inorgànica i Orgànica, Secció Inorgànica and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Martí i Franques 1-11, Barcelona, 08028, Spain.
Abstract:
The systematic reactions of a family of tetradentate pyridyl/imine and quinolyl/imine racemic or enantiopure Schiff bases with Ni(NO3 )2 or Ni(ClO4 )2 in the presence of sodium azide yielded, as a function of the starting racemic, chiral or achiral base, a set of chiral, meso or achiral complexes. In all cases, the compounds consist of two NiII cations linked by a double azido bridge in its end-on coordination mode. All the dimers exhibit a mesocate supramolecular structure and one of them, the unprecedented mix of helicate and mesocate in 2:1 ratio. The transition from mesocate to helicate conformation has been reached by tuning the flexibility of the central spacers of the Schiff bases and the size of the substituents. Electronic circular dichroism (ECD) studies have been performed for two pairs of enantiomers and interpreted by means of DFT calculations. Susceptibility measurements show a ferromagnetic coupling between the NiII cations mediated by the end-on azido bridges.
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