Coordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands

The synthesis of mixed-ligand complexes of the type [M₂L(μ-L')]⁺, where L represents a 24-membered macrocyclic hexaaza-dithiophenolate ligand, L' is an azobenzene carboxylate co-ligand, and M = Cd(II), Ni(II) or Zn(II), is reported. A series of new complexes were synthesized, namely [M₂L(μ-L')]⁺ (L' = azo-H, M = Cd (1), Ni (2); L' = azo-OH, M = Zn (3), Ni (4); L' = azo-NMe₂, M = Zn (5), Cd (6), Ni (7); L' = azo-CO₂Me, M = Cd (8), Ni (9)), and characterized by elemental analysis, electrospray ionization mass spectrometry (ESIMS), IR, UV-vis and NMR spectroscopy (for diamagnetic Zn and Cd complexes) and X-ray single crystal structure analysis. The crystal structures of 3' and 5-8 display an isostructural series of compounds with bridging azobenzene carboxylates in the trans form. The paramagnetic Ni complexes 2, 4 and 7 reveal a weak ferromagnetic exchange interaction with magnetic exchange coupling constant values between 21 and 23 cm^-1 (H = -2JS₁S₂). Irradiation of 1 with λ = 365 nm reveals a photoisomerization of the co-ligand from the trans to the cis form.