Near-infrared luminescent open-shell π-conjugated systems with a bright lowest-energy zwitterionic singlet excited state.

Open-shell systems with extensive π-conjugation have fascinating properties due to their narrow bandgaps and spin interactions. In this work, we report neutral open-shell di- and polyradical conjugated materials exhibiting intriguing optical and magnetic properties. Our key design advance is the planarized geometry allowing for greater interaction between adjacent spins. This results in absorption and emission in the near infrared at 803 and 1050 nanometers, respectively, and we demonstrate a unique electronic structure where a bright zwitterionic excited state is the lowest-accessible electronic transition. Electron paramagnetic resonance spectroscopy and superconducting quantum interference device measurements reveal that our materials are open-shell singlets with different degrees of spin interactions, dynamics, and antiferromagnetic properties, which likely contributed to the formation of their emissive zwitterionic singlet excited state and near-infrared emission. In addition, our materials show reversible and stable electrochromic switching with more than 500 cycles, indicating their potential for optoelectronic and electrochemical energy storage applications.

Structural and Dynamic Disorder, Not Ionic Trapping, Controls Charge Transport in Highly Doped Conducting Polymers.

Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counterions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique based on ion exchange, we prepare highly doped films with several counterions of varying size and shape and characterize their carrier density, electrical conductivity, and paracrystalline disorder. In this uniquely large data set composed of several classes of high-mobility conjugated polymers, each doped with at least five different ions, we find electrical conductivity to be strongly correlated with paracrystalline disorder but poorly correlated with ionic size, suggesting that Coulomb traps do not limit transport. A general model for interacting electrons in highly doped polymers is proposed and carefully parametrized against atomistic calculations, enabling the calculation of electrical conductivity within the framework of transient localization theory. Theoretical calculations are in excellent agreement with experimental data, providing insights into the disorder-limited nature of charge transport and suggesting new strategies to further improve conductivities.