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Effects on the aromaticity and on the biradicaloid nature of acenes by the inclusion of a cyclobutadiene linkage

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Abstract

Biphenylene is a well-characterized compound that includes the union of both aromatic and antiaromatic units: benzene and cyclobutadiene, respectively. In this work, we extend this structural theme to acene analogues with a cyclobutadiene linkage in a central position. At the single reference domain, perturbation theory and DFT calculations were applied to characterize the electronic structure of the extended biphenylene systems, as well as of some acenes of interest for comparison. Multireference calculations were also used to provide more accurate information about the energetic stability and insights into the radical character. Using descriptors such as the singlet–triplet splitting, the number of effectively unpaired electrons, fractional occupation number weighted density analysis and aromaticity indexes, the different compounds have been compared with respect to biradicaloid character and chemical stability through structural and energetic approaches. The results indicate that biphenylene derivatives should possess similar reactivities and stabilities as their half acenes fragments.

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Acknowledgments

The authors acknowledge the financial assistance of the Brazilian agencies Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) under Projects Nos. 307136/2019-1, 404337/2016-3, Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) under Project Process No. 2019/25105-6, and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) under Project CAPES/ITA No. 88882.161963/2014-01. FBCM, AJAA and HL are thankful to the FAPESP/Tianjin University SPRINT program (project No. 2017/50157-4) for travel support. The authors dedicate this work to Prof. Fernando Rei Ornellas for his excellence as an educator and supervisor, as well as for his leadership in the consolidation of the Computational Chemistry in Brazil.

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Authors and Affiliations

  1. Department of Chemistry, Instituto Tecnológico de Aeronáutica (ITA), 12228-900, São José dos Campos, São Paulo, Brazil

    Bruno D. Milanez, Julio C. V. Chagas, Max Pinheiro Jr & Francisco B. C. Machado

  2. Department of Mechanical Engineering, Texas Tech University, Lubbock, TX, 79409, USA

    Adelia J. A. Aquino

  3. School of Pharmaceutical Science and Technology, Tianjin University, Tianjin, 300072, People’s Republic of China

    Adelia J. A. Aquino & Hans Lischka

  4. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, 79409-1061, USA

    Hans Lischka

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  1. Bruno D. Milanez
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  2. Julio C. V. Chagas
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  3. Max Pinheiro Jr
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  4. Adelia J. A. Aquino
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  6. Francisco B. C. Machado
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Correspondence to Hans Lischka or Francisco B. C. Machado.

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Milanez, B.D., Chagas, J.C.V., Pinheiro Jr, M. et al. Effects on the aromaticity and on the biradicaloid nature of acenes by the inclusion of a cyclobutadiene linkage. Theor Chem Acc 139, 113 (2020). https://doi.org/10.1007/s00214-020-02624-w

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