Modulating Electronic Properties of Dinitrosoarene Polymers

23 February 2022, Version 3
This content is a preprint and has not undergone peer review at the time of posting.


Using the dinitrosobenzene polymer (1) as an example, we explore how the electronic, transport, and optical properties of a conjugated organic semiconductor can be modulated. Combining computational and experimental tools, we explore the effects of solid-state packing, backbone torsion, surface adsorption, the conjugation in the aromatic core, and substituents. The band gap (Eg) and optical spectrum of 1 are calculated using both GW-BSE with zero-gap renormalization (ZGR) and hybrid TD-DFT, with the former method predicting a value (2.41 eV) in excellent agreement with our diffuse reflectance spectroscopy measurements (2.39 eV). Using GW-BSE-ZGR, changes occurring upon solid-state packing are separated into a contribution arising from (i) the change in the torsional angle and (ii) the change in the screened Coulombic interaction, which strongly affects the exciton binding energies. Comprehensive hybrid TD-DFT calculations find that the effects of substituents on Eg and on transport properties can mostly be explained through changes in the torsional angle t, and predict a linear dependence between t and Eg. Extending the conjugation in the aromatic core is found to enhance transport properties and narrow Eg, identifying future synthetic targets. Atomic force microscopy and spectroscopic ellipsometry are used to study 1 adsorbed to a (111) gold surface (1@Au), with the latter method showing a significant narrowing of the band gap to 0.68 eV, in good agreement with TD-DFT predictions.


GW approximation
band gap engineering
organic polymers
organic semiconductors

Supplementary materials

Supplementary information for Modulating Electronic Properties of Dinitrosoarene Polymers
Supplementary information for the " Modulating Electronic Properties of Dinitrosoarene Polymers" manuscript, containing: (i) Optimized geometries of all structures (POSCAR) (ii) Benchmarking results for geometry optimization, GW calculations, and ZGR calculations. (iii) Calculated conductivity of C1, full phonon band structure of C1, TD-HSE predicted optical spectra, Hammett graph for dinitroso dimers and polymers.


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