Computational Insights into Tunable Reversible Network Materials: Accelerated ReaxFF Kinetics of Furan-Maleimide Diels-Alder Reactions for Self-Healing and Recyclability.

In this study, ReaxFF molecular dynamics simulations were benchmarked and used to study the relative kinetics of the retro Diels-Alder reaction between furan and -methylmaleimide. This reaction is very important for the creation of polymer networks with self-healing and recyclable properties, since they can be used as reversible linkers in the network. So far, the reversible Diels-Alder reaction has not yet been studied by using reactive molecular dynamics simulations.

Deciphering nonlinear optical properties in functionalized hexaphyrins explainable machine learning.

Over the years, several studies have aimed to elucidate why certain molecules show more enhanced nonlinear optical (NLO) properties than others. This knowledge is particularly valuable in the design of new NLO switches, where the ON and OFF states of the switch display markedly different NLO behaviors. In the literature, orbital contributions, aromaticity, planarity, and intramolecular charge transfer have been put forward as key factors in this regard.

Aromaticity in the Spectroscopic Spotlight of Hexaphyrins.

Spectroscopic properties are commonly used in the experimental evaluation of ground- and excited-state aromaticity in expanded porphyrins. Herein, we investigate if the defining photophysical properties still hold for a diverse set of hexaphyrins with varying redox states, topologies, peripheral substitutions, and core-modifications. By combining TD-DFT calculations with several aromaticity descriptors and chemical compound space maps, the intricate interplay between structural planarity, aromaticity, and absorption spectra is elucidated.

Application of Inverse Design Approaches to the Discovery of Nonlinear Optical Switches.

Molecular switches, in which a stimulus induces a large and reversible change in molecular properties, are of significant interest in the domain of photonics. Due to their commutable redox states with distinct nonlinear optical (NLO) properties, hexaphyrins have emerged as a novel platform for multistate switches in nanoelectronics. In this study, we employ an inverse design algorithm to find functionalized → redox switches with maximal βHRS contrast.

Designing hexaphyrins for high-potential NLO switches: the synergy of core-modifications and -substitutions.

Due to the enormous size of the chemical compound space, usually only small regions are traversed with traditional direct molecular design approaches making the discovery for novel functionalized molecules for nonlinear optical applications challenging. By applying inverse molecular design algorithms, we aim to efficiently explore larger regions of the compound space in search of promising hexaphyrin-based molecular switches as measured by their first-hyperpolarizability () contrast. We focus on the 28R → 30R switch with a functionalization pattern allowing for centrosymmetric OFF states yielding zero response.