Thiolate protected gold nanoclusters (NC) Aun(SR)m are a remarkable group of atomically precise structures in the field of noble metal nanoscience. This thesis aims to investigate the dynamic nature of gold clusters when exposed to external influences, such as free ligands. The knowledge obtained on ligand exchange reactions can be used to design new superstructures of clusters, either via controlled self-assembly by incorporation of a dithiol bridging agent or mechanical assembly by monolayer formation. The observed formation of communicating clusters gives interesting perspectives for the creation of novel properties which are absent in single NC.