This Ph.D. thesis describes the synthesis and structure of a series of organic and metalorganic molecules. The idea of the project was to combine the supramolecular properties of calixarenes with the catalytic properties of a metallocene. This was attempted by substitution at the upper rim of the calixarene with a metallocene. It proved however not possible to combine these two moieties. It was possible to substitute the upper rim of calixarene with two fluorenyl moieties and it was found by X-ray crystallography that the formation of a pentachloro zirconate tetrahydrofuran complex was obtained instead of the expected calixarene metallocene. By NMR and MALDI-TOF analysis it was proven that the transition metal tetrahalides are strong enough as Lewis acids to endorse the cleavage of one or more of the propoxy groups present at the lower rim of the calixarene. The anionic polymerization of styrene was investigated as a function of addition of crown-ethers and tetrapropoxy-calixarene and it was found the addition of crown-ethers strongly increased the reaction rate in the polymerization. In addition work is presented regarding the synthesis of 2,6,10-tris(tert-butyl)trioxatriangulene derivatised at the 12c-position and the synthesis of 7,8-dioxahelicene together with structural discussions originating from the X-ray structures.
|Place of Publication||Roskilde|
|Publisher||Risø National Laboratory|
|Number of pages||207|
|Publication status||Published - 2000|
|Series||Denmark. Forskningscenter Risoe. Risoe-R|