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Description:
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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 â  Hà º , and â  Sà º 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 . |