Dendritically encapsulated, water-soluble fe(4)s(4): synthesis and electrochemical properties

Amphiphilic, Fe(4)S(4) cluster core dendrimers can be prepared via ligand exchange with dendrons containing carboxylic acid peripheral groups and a thiol focal group. These amphiphilic dendrons are more susceptible to oxidative disulfide formation than their non-amphiphilic analogues reported previously. Thus, an in situ deprotection of an aromatic thioacetate was necessary to prepare the dendrimers. These molecules showed the expected decrease in rate with increasing generation. A slower rate of heterogeneous electron transfer was found when these molecules were compared with non-amphiphilic analogues. This behavior correlated with their larger size and thus a larger effective distance of electron transfer. Voltammetry in DMSO with added water makes the dendrimers easier to reduce, but the change in redox potential is much smaller for all dendrimers when compared to a non-dendritic analogue. This behavior is consistent with the idea that the dendrimers encapsulate the cluster to some degree, creating a hydrophobic microenvironment around the cluster.