Experimental assignment of long-range magnetic communication through Pd & Pt metallophilic contacts

Record-breaking magnetic exchange interactions have previously been reported for 3d-metal dimers of the form [M(Pt(SAc)₄)(pyNO₂)]₂ (M = Ni or Co) that are linked in the solid state via metallophilic Pt⋯Pt bridges. This contrasts the terminally capped monomers [M(Pt(SAc)₄)(py)₂], for which neither metallophilic bridges nor magnetic exchange interactions are found. Computational modeling has shown that the magnetic exchange interaction is facilitated by the pseudo-closed shell d⁸⋯d⁸ metallophilic interaction between the filled Pt²⁺ 5d orbitals. We present here inelastic neutron scattering experiments on these complexes, wherein the dimers present an oscillatory momentum-transfer-dependence of the magnetic transitions. This allows for the unequivocal experimental assignment of the distance between the coupled ions, which matches exactly the coupling pathway via the metallophilic bridges. Furthermore, we have synthesized and magnetically characterized the isostructural palladium-analogues. The magnetic coupling across the Pd⋯Pd bridge is found through SQUID-magnetometry and FD-FT THz-EPR spectroscopy to be much weaker than via the Pt⋯Pt bridge. The weaker coupling is traced to the larger radial extent of the 5d orbitals compared to that of the 4d orbitals. The existence of a palladium metallophilic interaction is evaluated computationally from potential surface cuts along the metal stretching direction. Similar behavior is found for the Pd⋯Pd and Pt⋯Pt-systems with clear minima along this coordinate and provide estimates for the force constant for this distortion. The estimated M⋯M stretching frequencies are found to match experimental observed, polarized bands in single-crystal Raman spectra close to 45 cm^-1. This substantiates the existence of energetically relevant Pd⋯Pd metallophilic interactions. The unique properties of both Pt²⁺ and Pd²⁺ constitutes an orthogonal reactivity, which can be utilized for steering both the direction and strength of magnetic interactions.