A μ3-Alkoxo-Bridged Tetranuclear [Cu4L2] Copper(II) Complex of a Hexadentate N2O4 Donor Ligand with a [6 + 0] Cu4O4 Cubane Core: Synthesis, Crystal Structure, and Magnetic Properties

• Published in: European Journal of Inorganic Chemistry 2010, Vol.2010 (22), p.3484-3490
• Main Authors: Maity, Dipankar, Jana, Atish D., Debnath, Mainak, Hearns, Nigel G. R., Sie, Ming-Han, Lee, Hon Man, Clérac, Rodolphe, Ali, Mahammad
• Format: Review
• Language: English
• Subjects: Chemical Sciences; Coordination chemistry; Copper; Magnetic properties; Material chemistry; N2O4 donor ligands
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201000095

A novel hexacoordinating non‐Schiff base ligand (H4L) with N2O4 donor atoms has been synthesized by simple Mannich reactions. The use of this ligand with Cu(ClO4)2·6H2O in different molar ratios as well as pH leads to the formation of a mononuclear species and a tetranuclear CuII complex possessing a cubane [Cu4L2] core with almost equal Cu···Cu separation. In the presence of an excess amount of copper(II) ions and triethylamine at reflux, the mononuclear [CuH2L] species can be converted into the tetranuclear one, whereas the reverse process was not observed even after prolonged reaction time. Both the complexes have been characterized by single‐crystal X‐ray diffraction and magnetic measurements. Magnetic studies reveal that complex 1 displays a paramagnetic Curie‐type behavior whereas 2 displays a singlet‐spin ground state induced by strong intramolecular antiferromagnetic interactions. A novel hexacoordinating non‐Schiff base ligand (H4L) with N2O4 donor atoms and its mono‐ and tetranuclear CuII complexeshave been synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements.