Structure Elucidation of 2D Polymer Monolayers Based on Crystallization Estimates Derived from Tip-Enhanced Raman Spectroscopy (TERS) Polymerization Conversion Data.

Structural elucidation of 2D polymer monolayers proving long-range order is a challenge that limits the pace in which this recent field of polymer chemistry and of synthetic 2D materials develops. To overcome this bottleneck, we here present a method in which tip-enhanced Raman spectroscopy is combined with a random growth crystallization model to obtain global features from local spectroscopic information. Concretely, we prove the nature and determine the conversion number X of the cross-links for two new 2D homopolymers and one (of three) new 2D copolymers. Assuming random and in-plane growth, our model results in crystallinity degrees of 93.1% to 99.7% and mean radii of defect-free crystalline areas of 3-15 nm for conversion numbers of 84% < X < 98%. Thus, we provide strong evidence for the synthetic monolayer 2D materials presented that they qualify as 2D polymers and are therefore perfectly suited for in-depth studies both in a more fundamental direction as well as toward application. This example shows how our method can affect current research on covalent sheets.