Ion-pairing-modulated magnetic properties of thiaporphyrin CuII complex cations.

The metal complexation of π-electronic systems with partial charge compensation for metal ions produces positively charged π-electronic systems that can act as building blocks for ion-pairing assemblies. In this study, the CuII complexation of thiaporphyrins was investigated to afford paramagnetic π-electronic cations that modulate ion-pairing assembly modes in combination with coexisting anions. Counteranion-dependent stacking modes regulated spin-spin interactions between the CuII complex cations, resulting in antiferromagnetic properties in the solid state.