Designing Magnetic Organic Lattices from High-Spin Polycyclic Units

This work addresses the conception of purely organic magnetic materials by properly bridging high-spin polycyclic hydrocarbons A and B, through covalent ligands L. The strategy varies two degrees of freedom that govern the magnetic character of the AL--B sequence, namely, the bridge response to spin polarization and the relative signs of spin density on carbon atoms to which the bridge is attached. Topological prescriptions based on Ovchinnikovs rule are proposed to predict ground-state spin multiplicities of various ALB sets. The relevance of these guiding principles is essentially confirmed through DFT calculations on dimers connected by conjugated bridges. The transferability of interunit magnetic couplings to larger assemblies is further checked, the building blocks tending to maintain their high-spin character whatever the environment. Such local designs open the way to periodic lattices of ferromagnetic, antiferromagnetic, ferrimagnetic, or paramagnetic materials.