Fractal aggregates of conjugated polymer in solution state

Semirigid conjugated polymers have received much scientific and technological interest due to their unique electrical and photonic semiconducting properties. Spectroscopic studies have indicated that these polymers underwent interchain aggregation in the solution state even at large dilution; however, the origin of this event and the structure of the resultant aggregates remained the crucial issues to be resolved. In the present study, we revealed that the interchain aggregation of a conjugated polymer, poly(2,3-diphenyl-5-hexyl-1,4-phenylenevinylene) (DP6-PPV), in solutions with chloroform and toluene generated network aggregates with the hydrodynamic radii of several micrometers. Small angle neutron scattering (SANS) demonstrated that the internal structure of these aggregates could be characterized by the mass fractal dimensions of 2.2-2.7. The networks were looser in chloroform but became highly compact in the poorer toluene solvent due to severe segmental association. Increasing the temperature alleviated the segmental association in toluene while largely retaining the mass fractal dimension of the aggregates. However, the interchain aggregation was never completely dissipated by the heating, suggesting the existence of two types of segmental association with distinct stability. The highly stable segmental association that could neither be solvated by chloroform nor be disrupted thermally in toluene was attributed to the d-d complex already present in the DP6-PPV powder used for the solution preparation. The chains tied firmly by this complex formed network aggregates in the solution and hence reduced the entropy of mixing of the polymer. In the poorer toluene solvent, further segmental association took place within the preexisting aggregates, making the networks more compact. This type of segmental association could be disrupted by moderate heating, and its occurrence was ascribed to the poor affinity of the aliphatic side chains of DP6-PPV for toluene.