DOI: 10.5061/dryad.nk98sf835
title: Data from: Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation

description: Controlling the reactivity of bonds along polymer chains enables both
 functionalization and deconstruction with relevance to chemical recycling
 and circularity. Because the substrate is a macromolecule, however,
 understanding the effects of chain conformation on the reactivity of
 polymer bonds emerges as important, yet underexplored. Here, we show how
 oxy-functionalization of chemically recyclable condensation polymers
 affects acidolysis to monomers through control over distortion and
 interaction energies in the rate-limiting transition states.
 Oxy-functionalization of polydiketoenamines at specific sites on either
 the amine or triketone monomer segments increased acidolysis rates by over
 three orders of magnitude, opening the door to efficient deconstruction of
 linear chain architectures. These insights substantially broaden the scope
 of applications for polydiketoenamines in a circular manufacturing
 economy, including chemically recyclable adhesives for a diverse range of
 surfaces.
description: # Circularity in polydiketoenamine thermoplastics via control over
 reactive chain conformation
 [https://doi.org/10.5061/dryad.nk98sf835](https://doi.org/10.5061/dryad.nk98sf835) ## Description of the data and file structure The archived files include one .ZIP `calculated_structures`.zip: Coordinates of the molecules used in the multi-path transition state theory calculations for diketoenamine (DKE) acidolysis described in *Theoretical Methods* in the Supplementary information, depicted in Figure 2 of the main text, and analyzed in Figures S1 and S2 of the Supplementary Information. There are two sub-directories: one for the reactant structures and one for the transition state structures. Coordinates are represented in the XYZ file format and are the final coordinates obtained from geometry optimization in Gaussian16 at the *ω*b97XD/6-311+G(d,p) level of theory with the solvent represented implicitly by the solvent model with density (SMD). * `./reactants` * This directory contains all reactant structures used in the calculations, as denoted by `_r_` in the file name. * Files beginning with `mX0` have **X** = 0a oxy-functionalization (DKE **1**) or site-specific oxy-functionalization within **X** = 1, 2, 3, or 4 conjoining bonds of the nitrogen (DKE **2**–**5**, respectively). * Files beginning with `m0X` have **X** = 0b oxy-functionalization (DKE **6**) or site-specific oxy-functionalization within **X** = 1, 2, or 3 conjoining bonds of the triketone (DKE **7**–**9**, respectively). * The final number in the file name differentiates the conformers of the molecule. * For example, `m10_r_10.xyz` is the 10th conformer of the reactant of DKE **2**, with oxy-functionalization within 1 conjoining bond of the nitrogen. * `./transition_states` * This directory contains all transition state structures used in the calculations, as denoted by `_ts_` in the file name. * Files beginning with `mX0` have **X** = 0a oxy-functionalization (DKE **1**) or site-specific oxy-functionalization within **X** = 1, 2, 3, or 4 conjoining bonds of the nitrogen (DKE **2**–**5**, respectively). * Files beginning with `m0X` have **X** = 0b oxy-functionalization (DKE **6**) or site-specific oxy-functionalization within **X** = 1, 2, or 3 conjoining bonds of the triketone (DKE **7**–**9**, respectively). * The final number in the file name differentiates the conformers of the molecule. * For example, `m10_ts_10.xyz` is the 10th conformer of the transition state of DKE **2**, with oxy-functionalization within 1 conjoining bond of the nitrogen.