Chloride ion-aided self-assembly of pseudoclathrochelate metal tris-pyrazoloximates.

Chloride ion-aided one-pot template self-assembly of a mixed pyrazoloxime ligand with phenylboronic acid on a corresponding metal(II) ion as a matrix afforded the first boron-capped zinc, cobalt, iron, and manganese pseudoclathrochelate tris-pyrazoloximates. The presence of a pseudocross-linking hydrogen-bonded chloride ion is critical for their formation, as the same chloride-capped complexes were isolated even in the presence of large excesses of bromide and iodide ions. As revealed by X-ray diffraction, all complexes are capped with a chloride ion via three N-H···Cl hydrogen bonds that stabilize their pseudomacrobicyclic frameworks. The MN6 coordination polyhedra possess a distorted trigonal prismatic geometry, with the distortion angles φ between their nonequivalent N3 bases of approximately 0°. Temperature dependences of the effective magnetic moment for the paramagnetic complexes showed the encapsulated metal(II) ions to be in a high-spin state in the temperature range of 2-300 K. In the case of the iron(II) pseudoclathrochelate, density functional theory (DFT) and time-dependent DFT calculations were used to assess its spin state as well as the (57)Fe Mössbauer and UV-vis-NIR parameters. Cyclic voltammetry studies performed for these pseudomacrobicyclic complexes showed them to undergo irreversible or quasi-reversible metal-localized oxidations and reductions. As no changes are observed in the presence of a substantial excess of bromide ion, no anion-exchange reaction occurs, and thus the pseudoclathrochelates have a high affinity toward chloride anions in solution.