Disentanglement of Surface and Confinement Effects for Diene Metathesis in Mesoporous Confinement

We study the effects of a planar interface and confinement on a generic catalytically activated ring-closing polymerization reaction near an unstructured catalyst. For this, we employ a coarse-grained polymer model using grand-canonical molecular dynamics simulations with a Monte Carlo reaction scheme. Inspired by recent experiments in the group of M. Buchmeiser that demonstrated an increase in ring-closing selectivity under confinement, we show that both the interface effects, i.e., placing the catalyst near a planar wall, and the confinement effects, i.e., locating the catalyst within a pore, lead to an increase of selectivity. We furthermore demonstrate that curvature effects for cylindrical mesopores (2 nm < d < 12.3 nm) influence the distribution of the chain ends, leading to a further increase in selectivity. This leads us to speculate that specially corrugated surfaces might also help to enhance catalytically activated polymerization processes.