Programming the assembly of carboxylic acid-functionalised hybrid polyoxometalates

We report here the straightforward synthesis and characterisation of a series Anderson-type hybrid polyoxometalates in high yield, functionalised with carboxylic acid following the reaction of anhydride precursors with the starting hybrid cluster ([n-N(C4H9)4]3[MnMo6O18((OCH2)3CNH2)2]). Seven new structures have been obtained, five of which have acid-terminated ligands. Six of these structures have been isolated with a yield higher than 80% with high purity. This reaction is limited by the bulkiness of the anhydride used; this effect can be employed to selectively synthesise one isomer out of three other possibilities. The acid groups and aromatic platforms attached to the clusters can act as building tools to bridge several length scales and engineer molecular packing within the crystal structure. The presence of acids should also change the hydrophilicity of the clusters, and therefore the way they interact with hydrophilic surfaces. We also show a potential relationship between the acid group interaction in the packing diagram and the cluster’s tendency to interact with a hydrophilic surface. In addition to reporting a derived synthetic path to new acid-terminated Mn-Anderson-type hybrids, we describe here a new way to program self-assembly motifs of these compounds in the crystal structure and at interfaces