The chemistry of rhodium(I) coordination complexes with hemilabile ligands

Coordination chemistry provides a means by which synthetic systems can be designed to mimic and possibly surpass biological ones in complexity and scope. Although these functional systems are getting more sophisticated, many fundamental questions still remain concerning the construction of such systems. This thesis is concerned with the investigation of RhI coordination complexes containing hemilabile ligands and the in situ fabrication of molecular transport junctions in the gaps of gold nanorods using the alkyne-azide click reaction. In the first part of this thesis, the effects of different environments (i.e. different solvents or temperatures) on the coordination geometry of RhI complexes are reported. In the second part of this thesis, the development of novel reactions that lead to heteroligated coordination environments of hemilabile ligands with transition metal ions is discussed. Finally, the synthesis of alkyne and azide functionalized molecules is discussed, which were used in the fabrication of molecular transport junctions in OLW-generated nanogaps.