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

Autor(es)

Milanez, Bruno D. ^[1] ; Chagas, V, Julio C. ; Pinheiro Jr, Max ; Aquino, Adelia J. A. ^{[2, 3]} ; Lischka, Hans ^{[4, 2]} ; Machado, Francisco B. C. ^[5]

Afiliação do(s) autor(es)

^[1] Inst Tecnol Aeronaut ITA, Dept Chem, BR-12228900 Sao Jose Dos Campos, SP - Brazil

^[2] Tianjin Univ, Sch Pharmaceut Sci & Technol, Tianjin 300072 - Peoples R China

^[3] Texas Tech Univ, Dept Mech Engn, Lubbock, TX 79409 - USA

^[4] Texas Tech Univ, Dept Chem & Biochem, Lubbock, TX 79409 - USA

^[5] Pinheiro Jr, Jr., Max, Chagas, Julio C., V, Inst Tecnol Aeronaut ITA, Dept Chem, BR-12228900 Sao Jose Dos Campos, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: THEORETICAL CHEMISTRY ACCOUNTS; v. 139, n. 7 JUN 16 2020.
• Citações Web of Science: 0

Resumo

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. (AU)

• Processo FAPESP: 19/25105-6 - Hidrocarbonetos aromáticos policíclicos (PAH's): dopagem, vacância, reatividade, estados excitados: uma abordagem multiconfiguracional
• Beneficiário: Francisco Bolivar Correto Machado
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 17/50157-4 - The development of biradicaloid systems and functionalized materials for organic semiconductors: accurate molecular information from multireference quantum theory
• Beneficiário: Francisco Bolivar Correto Machado
• Modalidade de apoio: Auxílio à Pesquisa - Regular