Data‐Driven Discovery of Organic Electronic Materials Enabled by Hybrid Top‐Down/Bottom‐Up Design

Abstract

The high‐throughput exploration and screening of molecules for organic electronics involves either a ‘top‐down’ curation and mining of existing repositories, or a ‘bottom‐up’ assembly of user‐defined fragments based on known synthetic templates. Both are time‐consuming approaches that require significant resources to compute electronic properties accurately. Here, we combine ‘top‐down‘ with ‘bottom‐up‘ through automatic assembly and statistical models and provide a platform for the fragment‐based discovery of organic electronic materials. We generate a top‐down set of almost 117K synthesized molecules containing their structures, electronic and topological properties and chemical composition, and use them as a building block library for bottom‐up fragment‐based design. A tool is developed to automate the coupling of these building blocks based on their available C(sp2/sp)‐H bonds, providing a fundamental link between the two philosophies of dataset construction. Statistical models are trained on this dataset and a subset of the resulting hybrid top‐down/bottom‐up compounds, enabling on‐the‐fly prediction of ground and excited state properties (frontier molecular orbital gaps, excitation energies) with high accuracy across known p‐block organic compound space. With access to ab initio‐quality optical properties, it is possible to apply this bottom‐up pipeline using existing compounds as building blocks to any materials design campaign. To illustrate this, we screen over a million molecular candidates for singlet fission, the leading candidates of which provide insight into the structural features promoting this multiexciton‐generating process.This article is protected by copyright. All rights reserved

Engineering Frustrated Lewis Pair Active Sites in Porous Organic Scaffolds for Catalytic CO2 Hydrogenation

“…After the initial refinement of these linker geometries at a semiempirical level of the theory (GFN2-xTB 35 ), a rigorous inhouse Python-based protocol was applied, in a bottom-up fashion, to automatically functionalize each of these linkers in all coupling sites with an acidic borane (-BR 2 ) fragment. 36 The amenable coupling sites are defined as sp 2 carbon atoms with available hydrogens, which were identified using a series of rules based on the connectivity of atoms in each linker geometry. This strategy is motivated by the well-established chemistry of the borylation of arenes, used in the context of FLP chemistry.…”

“…We begin with the top-down curation of 1043 organic linkers (seed linkers or SLs) from this database that have at least one exploitable nitrogen atom as a basic site in an FLP environment (see Section S1 for details of the linker curation). After the initial refinement of these linker geometries at a semiempirical level of the theory (GFN2-xTB), a rigorous in-house Python-based protocol was applied, in a bottom-up fashion, to automatically functionalize each of these linkers in all coupling sites with an acidic borane (-BR 2 ) fragment . The amenable coupling sites are defined as sp 2 carbon atoms with available hydrogens, which were identified using a series of rules based on the connectivity of atoms in each linker geometry.…”