Synthesis and characterization of a trinuclear CuII3 complex bridged by an extended phloroglucinol-ligand: implications for a rational enhancement of ferromagnetic interactions

Abstract

The synthesis and characterization of the extended phloroglucinol-ligand H₃felden based on the trialdehyde 2,4,6-triformylphloroglucinol and its trinuclear Cu^II₃ complex [(felden){Cu(bpy)}₃](ClO₄)₃ is presented. This study is motivated to optimize analogous extended phloroglucinol-ligands based on the triketone 2,4,6-triacetylphloroglucinol, which transmit ferromagnetic interactions by the spin-polarization mechanism between three Cu^II ions and have therefore been applied as the central ligand backbone for a class of heptanuclear single-molecule magnets in a supramolecular approach. A detailed NMR spectroscopic study reveals that the ligand H₃felden is not in the usually anticipated enol-imine form but in the tautomeric keto-enamine form. The presence of a C_3h and a C_s symmetric isomer results in a set of four different signals for each proton. In conjunction with FTIR, electronic absorption spectroscopy, and bond length considerations, it also appears that the complex [(felden){Cu(bpy)}₃](ClO₄)₃ must be considered as a resonance hybrid of an enolate-imine and a keto-enamine form. A strong contribution of the keto-enamine resonance structure with loss of the central π system explains the weak but ferromagnetic interactions between the Cu^IIS = 1/2 spins. This detailed analysis identifies the strong resonance with unsaturated groups in 2,4,6-position of phloroglucinol as the main source for the low ferromagnetic couplings by the spin-polarization mechanism in these ligands. This provides a synthetic handle to improve the spin-polarization mechanism in these ligands by replacing the imine with amine functions.