2020

Kolari, Kalle

This thesis titled ‘Metal-metal contacts in late transition metal polymers’ contains two main parts: the introductory section, and a section presenting and discussing the key results of the study. A concluding section, summarising the study’s findings, is also provided. The introduction gives a classification of metallopolymers based on parameters such as structure, metal-ion bonding interaction with the polymeric framework, and electronic interactions that polymers may express. Additionally, structural and crystal-packing features of metallopolymers— namely, extended metal atom chains (EMACs)—are presented. Moreover, first section of the thesis contains a brief introduction to metal-metal interactions. It also describes the solid state structure of compounds in which group 11 (Cu, Ag and Au), Rh, and Pt contacts with aromatic N, S-, or N-donor ligands are present. Finally, properties and applications of metal-metal contact containing compounds are presented. The second main part of thesis presents the results of the syntheses and characterisation of group 11, Rh, and Pt polymers. Either ditopic bridging ligands or chelating polypyridines were utilised to promote polymeric structures with close metal-metal contacts. Nine compouds were synthesized and characterized with single crystal x-ray diffraction. Metal-metal contacts were analysed with computational chemistry, distance criteria, or spectroscopy. Metal-metal distances with a sub sum of Bondi’s Van der Waals radii were present in 8 of obtained structures. In addition to Pt-Pt contacts, platinum polymer were found to be luminescent and act as a metallogelator. Fluorophilic interactions were found to impact on gelation behaviour of metallogelator. Mechanical and thermal stability and self-healing properties of obtained gel were investigated with rheology. In sum, the results presented highlight the great importance of ligand selection for the formation of structural and chemical features of one-dimensional polymeric materials that contain close metal-metal separations and interactions.