Direct Observation of Chain Lengths and Conformations in Oligofluorene Distributions from Controlled Polymerization by Double Electron–Electron Resonance

Synthetic polymers are mixtures of chains with different lengths, and their chain length and chain conformation are often experimentally characterized by ensemble averages. We demonstrate that double electron–electron resonance (DEER) spectroscopy can reveal the chain length distribution and the chain conformation and flexibility of the individual n-mers in oligo-(9,9-dioctylfluorene) from controlled Suzuki–Miyaura coupling polymerization. The required spin-labeled chain ends were introduced efficiently via a TEMPO-substituted initiator and chain-terminating agent, respectively, with an in situ catalyst system. Individual precise chain length oligomers as reference materials were obtained by a stepwise approach. Chain length distribution, chain conformation, and flexibility can also be accessed within poly­(fluorene) nanoparticles.