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Published on: December 16, 2013
Na(I)/Cu(I-II) heterometallic cages interconnected by unusual linear 2-coordinate OCN-Cu(I)-NCO links: synthesis,
Aurkie Ray1, Georgina M Rosair, Ramanan Rajeev
1Department of Chemistry, Jadavpur University, Raja S. C. Mullick Road, Kolkata, 700 032, India.
Abstract:
A new Na(I)/Cu(I-II) heterometallic coordination complex [Cu(2)L(2)Na(NCO)(2)Cu](n) (1) with an unusual architecture has been synthesised. In 1 cyclic Na-O-Cu-O-Cu cages constructed by the tetradentate N(2)O(2) donor Schiff base ligand (H(2)L = N,N'-bis(2-hydroxyacetophenone)propylenediimine) are interconnected to each other by a rare singly end-to-end bridged OCN-Cu(I)-NCO link generating 1D chain. The complex has been characterised by elemental, spectral and structural analysis. The cyclic voltammogram of 1 has been compared with the analogous complexes. Cryomagnetic susceptibility studies indicate the copper(II) centers in the cyclic Na-O-Cu-O-Cu cages are antiferromagnetically coupled with J = -13.8 cm(-1). Complex 1 is a new addition to a class of rare singly end-to-end cyanato bridged copper(I) species and interestingly the copper ions involved in OCN-Cu(I)-NCO links possess a linear 2-coordinate geometry. Density functional theory calculations have been carried out to gain additional insights into the metal and ligand orbitals participating in this unusual structure.
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