Twenty‐two samples of zinc carboxylates were prepared from saturated, non‐cyclic carboxylic acids with systematically altered hydrocarbon chain structures under well‐defined conditions. Essential temperature‐ and solvent‐induced changes concerning the coordination of the carboxylate group are shown using selected prepared samples, and general rules for systems containing zinc carboxylates in nonpolar media are presented. It is shown that there are three possible structural forms for zinc carboxylates: polymeric sheet, polymeric chain, and closed tetranuclear oxo complex molecules. These forms are closely related through their physical and chemical transitions. The results show that the spatial structure of the hydrocarbon chain is a crucial factor, besides physical and chemical conditions, limiting the possible forms of zinc carboxylates present in the system. The principles presented enable us to predict and design the behaviour of a system containing zinc carboxylate additives.

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A selection of stable Zn40(RCOO)6 complexes have been studied by FT-JR and FT-Raman spectroscopy. Polarised FT-Raman studies of two samples, which were in liquid state at ambient temperature, have also been completed. An attempt was made to construct the kinetic energy matrix for a simplified model involving 29 atoms with Td symmetry. A set of symmetry coordinates was chosen to describe the vibrational behaviour of the molecule and serve as a base for future force-field calculations. The characteristic frequencies of A1 and T2 species were assigned. Some of the E modes were also obtained.