Symmetry-guided monomer design enables the combinatorial synthesis and targeted screening of polyesters

Abstract

The rational design of polyester materials plays a crucial role in the development of functional polymers with tailored properties. In this work, we introduce a novel symmetry-guided molecular design strategy, which is a symmetry-aware, parameter-controlled design paradigm that both broadens and rationalizes the accessible chemical space of functional molecules. By introducing the concept of a pairwise atomic symmetry index (PASI) metric and applying targeted modifications to small molecules, a library of 10 614 diacids and 9983 diols is constructed, enabling a systematic and unexplored expansion of the chemical space of polyesters. The combinatorial pairing of these diacids and diols leads to the generation of over 100 million polyester structures. High-throughput prediction of the glass transition temperature (T_g) by the T_g-QSPR model aligns well with the typical thermal behavior in polyester materials. To validate the design methodology, a two-level verification process is performed. The predicted T_g values are first examined using molecular dynamics (MD) simulations and subsequently confirmed by differential scanning calorimetry experiments. The calculated T_g values show good agreement with both MD simulations (average absolute error (AAE) of 17.54 °C) and experimental measurements (AAE of 16.45 °C). These results further confirm the reliability and robustness of the proposed approach. This study not only provides an effective strategy for the large-scale generation of a polyester library and screening of property targeted polyesters, but also carries broader chemical implications beyond polyester design, offering potential insights for the development of functional molecules.