Trimeric perfluoro-ortho-phenylene mercury as a building block for supramolecular materials

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Title: Trimeric perfluoro-ortho-phenylene mercury as a building block for supramolecular materials
Author: Haneline, Mason Reames
Abstract: Trimeric perfluoro -ortho -phenylene mercury (1 ) constitutes one of the simplest trifunctional Lewis acidic hosts . Cooperative effects arising from the proximity of the mercury (II ) centers , the electron -withdrawing properties of the backbone and the accessibility of the electrophilic sites leads to the facile complexation of neutral and electron rich substrates . The planarity of the structure as well as its overall polarizability compounded with relativistic effects at mercury also permits the occurrence of non -covalent interactions . The main objective of this dissertation was to explore the potential of 1 as a building block for supramolecular materials . Compound 1 was investigated using single crystal x -ray diffraction and was found to display a rich polymorphism . The electronic structure , probed by DFT methods , shows that the LUMO of 1 has a large contribution from the mercury 6p orbitals and features a large lobe protruding above and below the center of the trinuclear mercury core . Complexes in which two nitronyl nitroxide radicals (NIT -Ph = 2 - (phenyl ) -4 ,4 ,5 ,5 -tetramethylimidazoline -1 -oxyl -3 -oxide ) coordinate to the trinuclear core of 1 above and below the Hg3 plane reveal that 1 does not significantly mediate magnetic interactions . The ability of 1 to complex & #960 ; -basic molecules such as tetrathiafulvalene (TTF ) , toluene , o -xylene , m -xylene , p -xylene , mesitylene , biphenyl , naphthalene , acenaphthalene , anthracene , pyrene , triphenylene , perylene , and coronene was also investigated and show that 1 and arenes form extended binary stacks in which the two components alternate . The photoluminescence observed in some of these supramolecular complexes corresponds to the phosphorescence of the arene indicating a mercury heavy atom effect . Complexation of 1 in solution was observed with hexaalkoxytriphenylenes (HATn , n = 1 , 6 ) by fluorescence and NMR spectroscopy . Finally , compound 1 forms electrophilic double sandwich structures with ferrocene and nickelocene in which a molecule of 1 caps each of the Cp ligands . The nickelocene adduct is stabilized towards oxidation , and the photophysical and magnetic properties indicate the occurrence of a mercury heavy atom effect .
URI: http : / /hdl .handle .net /1969 .1 /3290
Date: 2006-04-12

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Trimeric perfluoro-ortho-phenylene mercury as a building block for supramolecular materials. Available electronically from http : / /hdl .handle .net /1969 .1 /3290 .

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