A chiral alkali metal capped Ni4 cubane complex: synthesis, structure, magnetic and catalytic bromination studies

Abstract

A new chiral NaO2Ni4O2N2 cluster has been developed with a distorted capped cubane-type structure. The structure was determined by single crystal X-ray diffraction. The tetradentate Schiff-base ligand was synthesized by the condensation of o-vanillin and D-(-)‑threo-2-amino-1-(4-nitrophenyl)-1,3-propanediol. X-ray structure reveals that the complex possesses a Ni4 cubane cluster where sodium ion is anchored on the face of the cubane structure. Continuous shape measurement studies revealed that all the Ni centres are in distorted octahedral geometry and sodium ion adopts the spherical square pyramidal geometry. Further structural exploration reveals that the complex shows local distortions of the coordination geometries at each metal site, and these distortions govern the magnetic anisotropy associated with each NiII ion. For the present case, an elongation (dstr > 0) of the octahedral coordination sphere results in a local easy-plane anisotropy, with a positive DNi(II) parameter. Temperature dependant magnetization measurements showed a predominant ferromagnetic interaction amongst the four Ni centres. This complex is also catalytically active towards bromination of aromatic phenolic compounds. Initial catalytic activity was verified with the conversion of phenol red to bromophenol blue. Different phenolic substances show good conversion to their corresponding bromo derivatives. The complex showed good catalytic activity towards bromination of aromatic phenolic compounds, offering up to 99% conversion with 100% selectively to their corresponding bromo derivatives.