Paradoxical design of a serendipitous pyrazolate bridging mode: a pragmatic strategy for inducing ineluctable...

In this contribution we have carried out a systematic magnetostructural investigation to establish a robust one-to-one correlation between the quasi-orthogonal bridging mode of a pyrazolate ring and ferromagnetic coupling. Generating a complex with an elusive quasi-orthogonal pyrazolate bridging is a challenging task but would ineluctably result in a ferromagnetic exchange pathway. Notwithstanding the rarity, we report herein a series of bis-pyrazolato copper complexes. We have successfully exploited a so-called hypothetical-deductive model on a particular set of ligand systems that forced the pyrazolate moiety to adopt an unusual bridging mode with the M-Npz-Npz-M torsion angles in the range from 49.7° to 72.8°. The corroborating variable temperature direct current (DC) magnetic susceptibility data unequivocally confirm the ferromagnetic coupling for the complexes with the torsion angles greater than 71.37°. Furthermore, the experimental results are in excellent agreement with theoretical calculations. Based on density functional theory (DFT) calculations, again a one-to-one correspondence is made between the ligand structure and magnetic behaviour. The diradical character (y0) of the complexes is correlated with the extent of bonding interactions between the Cu centers and hence, their ferromagnetic or antiferromagnetic nature. The broken symmetry (BS) calculations on the magnetically active molecular orbitals indicate the essential magnetic behaviour of the complexes, while the EPR g-tensor calculations confirm that dx2-y2 is the magnetic orbital.