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.