Investigation of a molecular morphology effect on polyphenylazomethine dendrimers; physical properties and metal-assembling processes.

A series of novel dendritic polyphenylazomethines (DPA) with asymmetric morphologies was synthesized. Their physical properties, such as encapsulating effect, molecular dynamics, and metal assembly, are strongly dependent on the entire conformation of the molecules. The most important property is layer-by-layer metal assembly in the dendrimer structure from the core to the outside. Bis- and tris-substituted DPAs of the fourth generation also act as frameworks for stepwise assembly of a metal component (SnCl2), like the fully substituted symmetric DPA. However, extensive investigation of metal assembly in specific DPAs revealed that they do not follow the stepwise process. The molecular density calculated from the experimental hydrodynamic volume indicated that bis- and tris-substituted DPAs with asymmetric morphology still retain a free space similar to that of fully substituted symmetric DPA. The monosubstituted DPA, however, displayed a slightly higher density (smaller space) than the other DPAs. The experimental results suggest a bent conformation of the dendrimer in which the core moiety is folded into the dendron structure. In addition, the molecular dynamics were probed by means of the 1H NMR signals of the porphyrin core. It was demonstrated that the conformation is not fixed at room temperature in solvated DPAs, especially in monosubstituted DPA. A similar observation was for the smaller DPAs (third generations) with asymmetric morphologies. These dendrimers do not follow the stepwise complexation process. The structures of bis- and tris-substituted dendrimers which accurately follow the stepwise process are fixed. These observations provide a new insight into the finely controlled metal-assembly chemistry of dendritic macromolecules, and a rigid and fixed conformation is one of important factors for their unique properties.