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Absorption spectra of p–nitroaniline derivatives: charge transfer effects and the role of substituents

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Abstract

Context

Push–pull compounds are model systems and have numerous applications. By changing their substituents, properties are modified and new molecules for different applications can be designed. The work investigates the gas-phase electronic absorption spectra of 15 derivatives of push–pull para–nitroaniline (pNA). This molecule has applications in pharmaceuticals, azo dyes, corrosion inhibitors, and optoelectronics. Both electron-donor and electron-withdrawing groups were investigated. Employing machine learning–derived Hammett’s constants σm, σm0, σR, and σI, correlations between substituents and electronic properties were obtained. Overall, the σm0 constants presented the best correlation with HOMO and LUMO energies, whereas the σR constants best agreed with the transition energy of the first band and HOMO–LUMO energy gap. Electron-donors, which have lower σR values, redshift the absorption spectrum and reduce the HOMO–LUMO energy gap. Conversely, electron-withdrawing groups (higher σR’s) blueshift the spectrum and increase the energy gap. The second band maximum energies, studied here for the first time, showed no correlation with σ but tended to increase with σ. A comprehensive charge transfer (CT) analysis of the main transition of all systems was also carried out. We found that donors (lower σ’s) slightly enhance the CT character of the unsubstituted pNA, whereas acceptors (higher σ’s) decrease it, leading to increased local excitations within the aromatic ring. The overall CT variation is not large, except for pNA–SO2H, which considerably decreases the total CT value. We found that the strong electron donors pNA–OH, pNA–OCH3, and pNA–NH2, which have the smallest HOMO–LUMO energy gaps and lowest σ’s, have potential for optoelectronic applications. The results show that none of the studied molecules is fluorescent in the gas phase. However, pNA–NH2 and pNA–COOH in cyclohexane and water reveal fluorescence upon solvation.

Methods

We investigated theoretically employing the second-order algebraic diagrammatic construction (ADC(2)) ab initio wave function and time-dependent density functional theory (TDDFT) the gas-phase electronic absorption spectra of 15 derivatives of p–nitroaniline (pNA). The investigated substituents include both electron-donor (C6H5, CCH, CH3, NH2, OCH3, and OH,) and electron-withdrawing (Br, CCl3, CF3, Cl, CN, COOH, F, NO2, and SO2H) substituents.

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Data availability

The authors confirm that the data supporting the findings of this study are available within the article and its Supplementary Information (SI). Additional data are available in GitHub and Zenodo [120]. The Supplementary Information discusses the rationale for the choice of the substituent position, reviews the literature concerning the substituent’s influence on the absorption spectra, presents the vertical gas-phase spectra of all molecules, NTOs, correlations between Hammett’s constants and molecular properties, and xyz coordinates of the converged geometries.

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Acknowledgements

I. B. thanks the Brazilian agencies CNPq (Grant numbers 304148/2018-0 and 409447/2018-8) and FAPERJ (Grant number E26/201.197/2021) for support. M.M.C. thanks CAPES for a M. Sc. scholarship.

Funding

I.B. thanks the Brazilian agencies Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) through research grants 304148/2018–0 and 409447/2018–8 and Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro (Faperj) through grant E-26/201.197/2021 for the support of this research. Support for this research also came from the National Institute of Science and Technology on Molecular Sciences (INCT-CiMol) grant CNPq 406804/2022–2 and Nano Network grant FAPERJ E-26/200.008/2020. MMC thanks Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Capes) for a PhD scholarship.

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    Matheus Máximo-Canadas & Itamar Borges Jr.

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Matheus Máximo-Canadas: data curation, formal analysis, investigation, visualization, and writing—review and editing; Itamar Borges Jr: conceptualization, data curation, formal analysis, funding acquisition, methodology, project administration, resources, supervision, and writing—review and editing.

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Máximo-Canadas, M., Borges, I. Absorption spectra of p–nitroaniline derivatives: charge transfer effects and the role of substituents. J Mol Model 30, 120 (2024). https://doi.org/10.1007/s00894-024-05917-0

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