The Paramagnetic Properties of Breathing Metal-Organic Frameworks: Theoretical Models for Paddle-Wheel Secondary Building Units of Cobalt, Nickel, and Copper.

The metal-organic frameworks (MOFs) that contain paramagnetic metal cations at their secondary building units (SBUs) have potential applications in magnetic materials for single molecule magnets, molecular spintronics, and quantum computing. The quantum chemical investigations were carried out on the systems M(OCH) and M(OCH)(CHN2), which model paddle-wheel SBUs embedded in breathing paramagnetic MOFs, specifically M(bdc)(dabco) (dabco = CHN, bdc = CHO , M = Co, Ni, Cu). An analysis of the electronic states and interatomic interactions for these models was performed and compared with experimental data on heat capacity and magnetic susceptibility of M(bdc)(dabco). It is shown that the antiparallel ordering (broken symmetry) of the spins on the metal atoms is the lowest spin state of the model systems. The coordination of the dabco molecules makes the high-spin state the second most stable spin state, with a relatively small energy separation from the broken symmetry solution.