The isolation and full characterization of multinuclear Schiff base complexes is reported, and their relevance as precursors for octanuclear Zn8 salen cluster complex formation is discussed. Starting from simple precursors, three tetranuclear Zn4 complexes were accessed that incorporate typical half-salen units and comprise of bridging acetates. The use of alternative reaction conditions or a step-wise approach smoothly leads to Zn8 cluster formation. In addition, the tetranuclear Zn4 complexes themselves may also serve as precursors toward Zn8 cluster formation when treated under appropriate reaction conditions. The influence of the solvent medium in the latter Zn4 → Zn8 conversion was separately studied and revealed the formation of unusual pyridine-ligated multinuclear structures with fully condensed salen coordination pockets, providing a possible prelude to octanuclear cluster formation.
