Piotr Zabierowski

Cobalt(II) and copper(II) supramolecular networks with a 1-iminoisoindoline asymmetric pincer

The first synthesis and characterization of cobalt(II) and copper(II) complexes with an in situ prepared novel asymmetric trinitrogen isoindoline-based pincer type ligand, N-(2-picolyl)isoindoline-1-(2-picolyl)imine (pap), are reported. Single-crystal X-ray structures of the cis-[M(pap)Cl2] (M = Cu, Co) complexes reveal the presence of rare seven-membered chelate rings as well as various coordination geometries and packing modes. The water-soluble complexes were found to react with dicarboxylate ions, terephthalate (ta) and succinate (suc), forming three new compounds {[M(H2O)(pap)]2(μ-ta)}·ta·xH2O (M = Cu and Co) and {[Co(pap)(suc)]·xH2O}n. Their single-crystal X-ray structures are reported and discussed. The rigid ta ions facilitate the formation of binuclear hydrated supramolecular frameworks, whereas the flexible suc linker binds [Co(pap)]2+ moieties into 1D zigzag chains. The chains are non-covalently organized into a supramolecular network. The bulky pincer ligand, responsible for the luminescent properties, was found to be inert in these reactions and to facilitate a unique supramolecular architecture through π–π stacking interactions. The compounds presented in this work may have wider applicability, as molecular building blocks, in the construction of either discrete polynuclear clusters or extended networks with desirable properties.

Templated metalophilicity: synthesis of halometallic double salts directed by a dicopper(I) hydrazinyl-tetraimine nanocation

A nanometric size dication [Cu2(dih)2]2+ (where dih – 1,2-di[[2-(pyridin-2-yl)hydrazin-1-ylidene]methyl]benzene) of a molecular volume of 0.5 nm3 is described. The solvothermal synthesis and crystal structures of a new class of inclusion double salts, exhibiting d10–d10 and d10–d5 metallophilicity, of the formula [Cu2(dih)2]2[Cu(4 − y)MyCl8], where M is either Cu+ or heterometal of valency y (in this paper Mn2+ or La3+), are reported. UV-vis spectroscopy and square-wave voltammetry complement the characterisation of the luminescent salts.