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.

Five copper zinc phenylchalcogenolate complexes [(iPr 3 PCu) 3 (ZnMe 2 ) 2 (SPh) 3 ] (1), [(iPr 3 PCu) 2 (ZnPh) 4 (SPh) 6 ] (2), [(iPr 3 PCu) 2 (ZnEt) 4 (SPh) 6 ] (3), [(iPr 3 PCu) 3 (ZnEt)(SePh) 4 ] (4), and [(iPr 3 PCu) 3 Cu(iPr 3 PZn)(TePh) 6 ] (5) were synthesized by the reaction of phosphine stabilized copper phenylchalcogenolate complexes with ARTICLE Scheme 1. Reactions starting from [iPr 3 PCuSPh] 3 , [(iPr 3 P) 4 (CuSePh) 6 ] or [(iPr 3 P) 3 (CuTePh) 4 ] with ZnR 2 (R = Me, Et, Ph) with and without additional chalcogenol.

The complex [Ni2L]2+ exhibits a pre-organized binding pocket, whose walls direct the coordination of pseudohalide ions via repulsive CH⋯π interactions.

The synthesis, structure and photophysical properties of two polynuclear zinc complexes, namely [Zn6L2(µ3-OH)2(OAc)8] (1) and [Zn4L4(µ2-OH)2](ClO4)2 (2), supported by tridentate Schiff base ligand 2,6-bis((N-benzyl)iminomethyl)-4-tert-butylphenol (HL) are presented. The synthesized compounds were investigated using ESI-MS, IR, NMR, UV-vis absorption spectroscopy, photoluminescence spectroscopy and single-crystal X-ray crystallography. The hexanuclear neutral complex 1 comprises six-, five- and four-coordinated Zn2+ ions coordinated by O and N atoms from the supporting ligand and OH- and acetate ligands. The Zn2+ ions in complex cation [Zn4L4(µ2-OH)2]2+ of 2 are all five-coordinated. The complexation of ligand HL by Zn2+ ions leads to a six-fold increase in the intensity and a large blue shift of the ligand-based 1(π-π)* emission. Other biologically relevant ions, i.e., Na+, K+, Mg2+, Ca2+, Mn2+, Fe2+, Co2+, Ni2+ and Cu2+, did not give rise to a fluorescence enhancement.