Crystal Induced Selectivity
Creators: name: Sundberg, Jonas
Publisher: name: figshare
Year: 2024
Subjects: classificationCode: 340209
subject: Organometallic chemistry
classificationCode: 340211
subject: Transition metal chemistry
classificationCode: 340301
subject: Inorganic materials (incl. nanomaterials)

description: This thesis, and the data presented herein describes work primarily done under the supervision of Christine McKenzie, University of Southern Denmark between the pe- riod of January 2009 to April 2013. During July to 2010 and April 2011 I worked un- der the combined supervision of Christine McKenzie and Mikael Håkansson at The University of Gothenburg, Sweden. During February to April 2012 I was working in collaboration with Prof. Cameron Kepert at The University of Sydney, Australia.<br><b>ABSOLUTE ASYMMETRIC SYNTHESIS</b>As the generation of enantiomerically pure inorganic and organic compounds are of utter importance, for example not only in the pharmaceutical industry, but as optical materials and other industrially used chemicals. The interest in preparation of optically pure compounds have since its discovery been a very active area of research. I, however is not interested in practical applicability of compounds but of the underlying chemistry of them and how they behave on a molecular level. Herein this thesis, the goal has been to present otherwise unconventional methods for asymmetric synthesis exploiting geometrical organizations in the solid state. The configurational lability of chirality surrounding a stereogenic atom may differ heavily. In this work we have demonstrated how coordination compounds with achiral thioether ligands, through their arrangement in the solid state may form “temporary” stereogenic arrangements. By further transformations, this “temporary” chirality is fixated using reagents which transforms the initially achiral ligand molecules to configurationally stable enantiomers. Therefore, through solid-state chemistry we have demonstrated how asymmetric transformation can occur without the use of any other pre-formed chirality or auxiliaries while leading to enantioenriched end products.<br>Not only has such asymmetric synthesis been demonstrated, throughout the work we have synthesized and characterized a large volume of previously unknown coordination compound, which have gained insight into the solid state structures and how metal atoms interact with organic molecules under different conditions. Not only have it allowed further elucidation of molecular interactions in the crystalline lattice, but also how metal atoms can activate for example molecular oxygen leading to new types of reactions.<br><b>REVERSIBLE OXYGEN CHEMISORPTION</b>We have not only shown that the solid state properties of compounds may be used for the selective transformation of reactants, but also how they interact with small- type molecules. The separation of gases is an important large-scale industrial pro- cess, that from several viewpoints lack refinement to meet the requirements of to- days industrial processes. In order to further the understanding of how molecular compounds can interact, bind and modify atmospheric gases we have prepared an extended set of previously unknown cobalt-based oxygen carriers to see how their properties may be tuned in regards to oxygen affinity and selectivity