Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging Quinn T. Easter Antonio Garcia Suzanne A. Blum 10.1021/acscatal.9b00095.s005 https://acs.figshare.com/articles/media/Single-Polymer_Particle_Growth_Kinetics_with_Molecular_Catalyst_Speciation_and_Single-Turnover_Imaging/7853246 The dynamics of the local environments surrounding molecular polymerization catalysts plausibly impact turnover kinetics, but the impact of and nature of such dynamics have previously been obscured by ensemble averaging. With Grubbs’ second generation ruthenium metathesis catalyst and a precipitation polymerization system, studies at the single-particle and -turnover level establish that (1) an inverse correlation exists between rate and duration of single-polymer–particle growth of aggregates, consistent with a local environment density model for the time-variable kinetics; (2) cross-linking additives produced a small, but detectible, reduction in overall monomer incorporation; (3) total ruthenium quantity within the polymer particles (as characterized by energy dispersive X-ray spectroscopy) is differentiable from the quantity that is catalytically active (as characterized by in situ fluorescence microscopy), providing catalyst speciation information; and (4) time-resolved enyne metathesis reactions can be imaged, corresponding to single turnovers at individual molecular catalysts during polymer growth under synthetically relevant conditions. These findings identify and characterize reactivity distributions likely arising from the dynamics of local environments. As such, these data provide reactivity information that is unavailable through traditional ensemble analytical methods that obscure this type of information through averaging. 2019-03-04 00:00:00 dynamic environment density model polymerization catalysts precipitation polymerization system catalyst speciation information energy dispersive X-ray spectroscopy Molecular Catalyst Speciation generation ruthenium metathesis catalyst reactivity information impact turnover kinetics polymer growth time-variable kinetics turnover level reactivity distributions Single-Turnover Imaging monomer incorporation ruthenium quantity ensemble polymer particles