Exploring structural, magnetic, and catalytic diversity in tetranuclear {Cu4O4} cubane cores and a dinuclear complex
Narayan Ch Jana1, Albert Escuer2,3, Paula Brandão4
1Department of Chemistry, Panskura Banamali College, Panskura RS, WB 721152, India. ampanja@yahoo.co.in.
Abstract:
The coordination compounds featuring a {Cu4O4} core, typically bridged by hydroxo or alkoxo groups, are particularly intriguing due to their notable magnetic properties and catalytic activity. In this study, we explored the synthesis and characterization of four new Schiff base ligands and their subsequent complexation with CuII salts, which resulted in the formation of three tetranuclear complexes: [Cu4(L1)4]·2H2O (1), [Cu4(L2)2(HL2)2](Cl)(NO3)·5H2O (2), and [Cu4(L3)4] (3), as well as one dinuclear complex: [Cu2(L4)2] (4). These tetranuclear complexes all feature a {Cu4O4} core, but with differing coordination environments around the CuII centers. For instance, complex 1 exhibits μ3-phenoxido bridges and a distorted octahedral geometry, while complex 3 features μ3-alkoxido bridges and a square pyramidal geometry. Complex 2 displays an open cubane core with mixed μ2-phenoxido and μ3-alkoxido bridges, with both square planar (CuNO4) and octahedral (CuNO5) geometries. In addition, dinuclear complex 4 was synthesized, featuring square planar CuII centers linked by μ2-alkoxido bridges. The magnetic studies revealed that 1 and 2 exhibit strong antiferromagnetic coupling, which is attributed to their larger Cu-O-Cu bond angles, while complex 3 demonstrates moderate ferromagnetic behavior, associated with smaller bond angles. Literature reports indicate that {Cu4O4} cubane cores generally show ferromagnetic interactions at bond angles near 104°, but in complex 3, we observed moderate ferromagnetic interactions with a Cu-O-Cu bridging angle of 108.41(9)°, making it one of the highest bond angles observed for ferromagnetic interactions in a {Cu4O4} cubane-like system. The planar dinuclear complex 4 exhibits extremely strong antiferromagnetic coupling, which is attributed to the ideal Cu-O-Cu bridging angles and the planar Cu-O-O-Cu core. Additionally, EPR measurements of complex 3 at 4 K reveal a well-isolated S = 2 ground state, separated by a gap of 65.8 cm-1 from the three closest degenerate spin levels (S = 0, 1, and 1). Finally, all four complexes were used as catalysts for the aerobic oxidation of 2-aminophenol, and the mechanism of the oxidation process was elucidated by EPR spectroscopy.
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