Supramolecules with dimolybdenum or chiral dirhodium units

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Title: Supramolecules with dimolybdenum or chiral dirhodium units
Author: Yu, Rongmin
Abstract: This dissertation concerns the syntheses and characterization of supramolecules with quadruply bonded Mo2 4+ units , Mo2 (DAniF )3 + (DAniF = N ,N' -di -p -anisylformamidinate ) or cis - Mo2 (DAniF )2 2+ , and chiral organometallic Rh2 4+ units , including racemic cis -Rh2 (C6H4PPh2 )2 2+ and pure enantiomers of cis -Rh2 (C6H4PPh2 )2 2+ . Molecular pairs of dimolybdenum units in which Mo2 (DAniF )3 + units are linked by cyclic diamidate anions or dioxolene anions have been investigated . Linkers impact the electronic communication between the dimetal units in various ways . The symmetry and the energy of the frontier orbitals of the linker are among the factors which influence significantly the properties of the molecular pairs . Nature has provided us a great opportunity to study quantitatively the equilibrium between neutral supramolecules with cis -Mo2 (DAniF )2 2+ units . Studies of the concentrationdependent and temperature -dependent equilibria between a molecular triangle and square as well as a molecular loop and triangle using 1H and 19F NMR spectra provide quantitative values for the thermodynamic equilibrium constant K , as well as ? ? ? ? ? ?H ? ? ? ? , and ? ? ? ? ? ?S ? ? ? ? for the equilibria . The synthesis and characterization supramolecular compounds containing chiral cis - Rh2 (C6H4PPh2 )2 2+ units , including three racemic triangles and pure enantiomers of three triangles , a carceplex with T symmetry and two loops are also presented .
URI: http : / /hdl .handle .net /1969 .1 /4794
Date: 2007-04-25

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Supramolecules with dimolybdenum or chiral dirhodium units. Available electronically from http : / /hdl .handle .net /1969 .1 /4794 .

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