Christian Schütt, Gernot Heitmann, Thore Wendler, Bahne Krahwinkel, Rainer Herges


Light-switchable azoimidazoles were rationally designed and synthesized, and their performance was investigated as photodissociable ligands (PDL) and for spin state switching of Ni porphyrins. The rationally designed ligands exhibit a high photochemical conversion rate (trans → cis > 98%) and no measurable fatigue over a large number of switching cycles at room temperature under air. As compared to the known phenylazopyridines, the phenylazoimidazoles exhibit a much stronger affinity as axial ligands to Ni porphyrin in the binding trans configuration and a low affinity in their cis form. This affinity switching was used to control the coordination number of Ni2+. Concomitant with the change in coordination number is the change of the spin state from triplet (high spin) to singlet state (low spin). We report on phenylazoimidazole-based PDLs that switch the paramagnetic ratio of the investigated nickel species by up to 70%. Consequently, azoimidazoles exhibit considerably higher switching efficiencies than previously described pyridine-based PDLs.