12-metallocrown-4: A structural and functional inorganic analogue of 12-C-4.

摘要

etallacrowns are a class of inorganic molecular recognition agents which are analogous to crown ethers. The metallacrown analogy replaces the methylene units of crowns with transition metal-nitrogen linkages which leads to molecules with strong visible absorption spectra, paramagnetism and redox activity.;Generalizing the metallacrown analogy as a synthetic protocol for the preparation of multinuclear complexes required metallacrowns synthesized with various (1) organic ligands, (2) ring metals, (3) core metals and (4) bound anions in the predicted structural motifs. Chapter II discusses the synthesis of copper 12-metallacrown-4's from novel hydroxamic acid ligands, e.g. anthranilic hydroxamic acid, which alter the donor atoms and the peripheral organic architecture. Vanadium, iron, manganese, copper and gallium metallacrowns are synthesized from salicylhydroxamic acid derivatives. Alkali metal:halide complexes of the manganese 12-metallacrown-4 allow for comparison of the structural features influencing joint cation/anion binding. Comparisons of metallacrown, crown ether, phthalocyanine and porphyrin structures are made.;Chapter III defines the solution integrity and dynamics of the metallacrowns using electrospray ionization mass spectrometry, NMR spectroscopy (;Chapter IV establishes the metallacrown's functional analogy to crown ethers. Cation affinity