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Tweaking the conjugation effects on a pair of new triazene compounds by targeted deprotonation: a spectroscopic and theoretical overview

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Abstract

Context

Triazene compounds (-NNN(H)-) exhibit versatility in biological, physical, and chemical applications. In their anionic form (-NNN-)(-), they can act as coordinating sites for metals, forming metallic complexes. In this study, two new isomeric triazene compounds with meta- and para-substituents in their neutral and anionic forms were investigated. A combination of detailed experimental spectroscopic characterization and computational chemistry analyses were employed. The new compounds, 1-(2-benzamide)-3-(3-nitrophenyl) triazene (m-TZN) and 1-(2-benzamide)-3-(4-nitrophenyl) triazene (p-TZN), were compared to 1,3-diphenyltriazene (dph-TZN) to understand the effects of functionalization and targeted triazene deprotonation. The anionic forms are stable, and our investigation suggests that these new compounds are suitable tridentate ligands that can act as chelating agents for metallic cations in stable complexes, similar to those found in vitamin B12.

Methods

The absorption, vibrational, and electronic properties of the newly synthesized triazene compounds were extensively characterized using FT-IR/FT-Raman and UV-Vis spectroscopy. Their distinct molecular properties, intramolecular hydrogen bond effects, stability, and electronic transitions were investigated using the ORCA software. These analyses involved DFT and TD-DFT calculations at the ωB97X-D3/Def2-TZVP level of theory with THF CPCM implicit solvation to determine the molecular topology and electronic structure. The advanced STEOM-DLPNO-CCSD method for excited states was employed, enabling an in-depth analysis of ground and excited-state chemistry, accounting for precise electronic correlation and solvation effects. Explicit THF solvation was tested on the full TD-DFT ωB97X-D3/Def2-TZVP level and using ONIOM on the STEOM calculation. Reactivity was studied using Fukui functions, and action as chelating agents was investigated using GFN-xTB2 and DFT.

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Data availability

All relevant data generated or analyzed during the work are included in this paper and any additional data can be made available upon reasonable request.

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Acknowledgements

We thank Dr. Mariana Boneberger Behm (UFFS) and Dr. Manfredo Hörner (UFSM) for providing the m-TZN and p-TZN reactants. Theoretical calculations were performed using the Lobo Carneiro supercomputer from Núcleo Avançado de Computação de Alto Desemprenho (NACAD), under the Project ID a20006 and the Sagarana Cluster from CEPAD - Centro de Processamento de Alto Desempenho ICB/UFMG. The authors would also like to thank the National Laboratory for Scientific Computing (LNCC/MCTI, Brazil) for providing HPC resources of the SDumont supercomputer, which have contributed to the research results reported within this paper. URL: http://sdumont.lncc.br.

Funding

The authors would like to thank the funding from PROAP/CAPES, 001.

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Authors and Affiliations

  1. Universidade Federal do Rio Grande do Sul - Instituto de Química, Porto Alegre, RS, Brazil

    Henrique de Castro Silva Junior

  2. Programa de Pós-graduação em Ciência e Engenharia de Materiais, Universidade Federal do Pampa, Campus Bagé, Bagé, RS, Brazil

    Uhil Antunes & Eduardo Ceretta Moreira

  3. Centro de Ciências Químicas, Farmacêuticas e de Alimentos, Universidade Federal de Pelotas, Pelotas, RS, Brazil

    Aline Joana Rolina Wohlmuth Alves dos Santos

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  1. Henrique de Castro Silva Junior
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  2. Uhil Antunes
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  3. Aline Joana Rolina Wohlmuth Alves dos Santos
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  4. Eduardo Ceretta Moreira
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Contributions

H.C.: theoretical calculations, wrote the main manuscript text, figure preparation. U.A.: experimental FT-Raman/IR measurements, figure preparation. A.J: syntheses, funding, wrote the main manuscript text. E.C.: project management, experimental FT-Raman/IR measurements, FT-Raman/IR discussion, wrote the main manuscript text. All authors reviewed the manuscript.

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Correspondence to Henrique de Castro Silva Junior.

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de Castro Silva Junior, H., Antunes, U., dos Santos, A.J.R.W.A. et al. Tweaking the conjugation effects on a pair of new triazene compounds by targeted deprotonation: a spectroscopic and theoretical overview. J Mol Model 29, 298 (2023). https://doi.org/10.1007/s00894-023-05685-3

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