“Diluting branches” put to work: from synthesis to properties control of multifunctional polymers derived from triphenylamine, fluorene and thiophene†

A series of highly branched polymers was synthesized by Suzuki polycondensation of thiophene-, fluorene-, and triphenylamine-based monomers, following the “A₂ + B₂ + C₃” pathway. A “dilution of branches” approach allows branching density management and generates conjugated frameworks with linear, alkyl-decorated segments of various lengths. This strategy affects solubility, morphology, and thermal features and allows further control options. The building blocks are involved individually or in combinations in the main electronic transitions and charge and energy transfer processes, as confirmed by computational and experimental UV–vis and photoluminescence studies. The absorption and emission profiles are influenced by branching density, solvent, or the sample's physical state. The structural units’ particular arrangement in each branched construct regulates the redox patterns and electrochemical parameters. The polymers’ overall features and their variation with structure and branching density assemble the foundation for engaging conjugated materials for (opto)electronic applications.