Polymeric Frameworks as Organic Semiconductors with Controlled Electronic Properties

TL;DR

This study combines experimental electrochemical techniques and theoretical calculations to analyze how the composition and stacking of polymeric frameworks influence their electronic properties, aiding the design of tailored organic semiconductors.

Contribution

It provides a combined experimental and theoretical approach to understand and predict the electronic structures of 2D polymeric frameworks based on their composition and stacking.

Findings

Electronic properties depend on aromatic ring ratio.

Experimental density of states matches first principles calculations.

Stacking layers influence electronic structure.

Abstract

The rational assembly of monomers, in principle, enables the design of a specific periodicity of polymeric frameworks, leading to a tailored set of electronic structure properties in these solid-state materials. The further development of these emerging systems requires a combination of both experimental and theoretical studies. Here, we investigated the electronic structures of two-dimensional polymeric frameworks based on triazine and benzene rings, by means of electrochemical techniques. The experimental density of states was obtained from quasi-open-circuit voltage measurements through galvanostatic intermittent titration technique, which we show to be in excellent agreement with first principles calculations performed for two and three-dimensional structures of these polymeric frameworks. These findings suggest that the electronic properties do not only depend on the number of stacked layers but also on the ratio of the different aromatic rings.