New Calixarene and Cyclophane Macrocycles

The design, synthesis and analysis of new supramolecular hosts are rapidly developing areas of chemistry. This dissertation research presents the synthesis of new calix[4]arene ligands, new cyclophane derivatives and a new type of crown ether corrals accompanied by fluorescence binding analysis. A variety of calix[4]arene ligands have been developed in the past for various applications. Novel di-ionizable tetrabutoxycalix[4]arenes in four different conformations have been synthesized in this dissertation research. In contrast with the tetrabutoxycalix[4]arene ligands which are conformationally fixed, a conformationally mobile methoxy-tributoxy-calix[4]arene was synthesized. The synthetic exploration of calix[4]arene ligands was expanded into multicalix[4]arenes and cyclophane-bridged calix[4]arenes. Cyclophanes have been applied to diverse areas of supramolecular chemistry. A cyclophane with rigid α,α’-bis[(4-hydroxyphenyl]-1,4-diisopropyl-benzene components has been previously termed “corrals”. New synthetic routes, methods, techniques and ring-closure components have been applied to achieve 77 new corral derivatives, which selectively possess attractive properties, such as chirality, selective functionalization, asymmetry, and fluorescence. For some of the new cyclophane hosts synthesized fluorescence binding analysis was conducted. A total of 75 metal salt species was tested with two crown ether corrals resulting in interesting cation recognition, anion effects and selective fluorescence effects on shaking.