10.1021/ja9080452.s001 Stephan A. Schmid Stephan A. Schmid Robert Abbel Robert Abbel Albertus P. H. Schenning Albertus P. H. Schenning E. W. Meijer E. W. Meijer Rint P. Sijbesma Rint P. Sijbesma Laura M. Herz Laura M. Herz Analyzing the Molecular Weight Distribution in Supramolecular Polymers American Chemical Society 2009 chain lengths steplike process equivalent covalent polymers energy transfer dynamics equivalent Monte Carlo simulation PL Poisson function chain components oligofluorene units Supramolecular PolymersWe excitation energy growth process chain length distribution function weight distribution trial functions supramolecular chain supramolecular polymerization transition transfer rates Flory distribution chain end energy traps formation process polycondensation reactions Molecular Weight Distribution supramolecular building blocks polymer chains 2009-12-09 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Analyzing_the_Molecular_Weight_Distribution_in_Supramolecular_Polymers/2807290 We have investigated the formation process of supramolecular linear polymer chains and its influence on the resulting chain length distribution function. For this purpose, we explored the migration of excitation energy between oligofluorene units coupled together through quadruple hydrogen-bonding groups to form linear chains that are terminated by oligophenylene vinylene end-caps acting as energy traps. The energy transfer dynamics from the main chain to the chain end was monitored experimentally using time-resolved PL spectroscopy and compared to an equivalent Monte Carlo simulation incorporating information on the structure of the chains, the transition transfer rates, and various weight distribution trial functions. We find that the assumption of a Flory distribution of chain lengths leads to excellent agreement between experimental and simulated data for a wide range of end-cap concentrations. On the other hand, both a Poisson function and a simplified assumption of a monodisperse distribution significantly underestimate the presence of long chains in the ensemble. Our results therefore show that supramolecular polymerization is a steplike process equivalent to polycondensation reactions in linear covalent polymers. These findings emphasize that equal reactivity of the supramolecular building blocks leads to a dynamic growth process for the supramolecular chain involving all chain components at all times.