Repurposing DNA-binding agents as H-bonded organic semiconductors

Abstract

Organic semiconductors are usually polycyclic aromatic hydrocarbons and their analogs containing heteroatom substitution. Bioinspired materials chemistry of organic electronics promises new charge transport mechanism and specific molecular recognition with biomolecules. We discover organic semiconductors from deoxyribonucleic acid topoisomerase inhibitors, featuring conjugated backbone decorated with hydrogen-bonding moieties distinct from common organic semiconductors. Using ellipticine as a model compound, we find that hydrogen bonds not only guide polymorph assembly, but are also critical to forming efficient charge transport pathways along π−conjugated planes when at a low dihedral angle by shortening the end-to-end distance of adjacent π planes. In the π−π stacking and hydrogen-bonding directions, the intrinsic, short-range hole mobilities reach as high as 6.5 cm2V−1s−1 and 4.2 cm2V−1s−1 measured by microwave conductivity, and the long-range apparent hole mobilities are up to 1.3 × 10–3 cm2V−1s−1 and 0.4 × 10–3 cm2V−1s−1 measured in field-effect transistors. We further demonstrate printed transistor devices and chemical sensors as potential applications.

Pushing property limits in materials discoveryviaboundless objective-free exploration

“…In a similar attempt, the repurposing of deoxyribonucleic acid topoisomerase inhibitors as organic semiconductors has also been reported. 66 The results of our demonstration suggest that BLOX has the potential to accelerate the discovery of new materials by using databases collected for one purpose in other unintended elds.…”

Optimizing the self‐assembly of conjugated polymers and small molecules through structurally programmed non‐covalent control

“…In 2019, Zhang et al investigated how the hydrogen bond mediated self-assembly of ellipticine modulates the charge transport in ellipticine crystals. 65 Ellipticine (Figure 3) was chosen from a list of DNA topoisomerase inhibitors due to its calculated HOMO being similar to typical p-type organic semiconductors. Crystal structures of two polymorphs of ellipticine reveal distinct packing patterns featuring both short inter-chromophore separation and hydrogen bonding.…”

“…Reproduced with permission. 65 Copyright 2019, Nature Publishing Group electrical conductivity due to their insulating nature. Voorhaar and coworkers extended this approach to poly(thiophene-phenylenes) with similar results.…”

Sensing a binding event through charge transport variations using an aromatic oligoamide capsule

“…The investigation of charge transport through organic molecules and their use in electronics are well-established. 3 Nevertheless, the coupling of charge transport properties of a molecular junction to a binding signal is an essentially unexplored area of research and has remained focused on the use of biopolymers 4 or metal organic frameworks. 5 Substantial progress in this area has notably come from the incorporation of molecular receptors into the active layer of organic field-effect transistors or electrochemically using modified electrodes which, in the case of biological receptors, can be made to work in an aqueous environment.…”