Interplay between Aromaticity and Radicaloid Character in Nitrogen-Doped Oligoacenes Revealed by High-Level Multireference Methods

Autor(es)

Pinheiro, Jr., Max ^[1] ; Das, Anita ^[2] ; Aquino, Adelia J. A. ^{[3, 2, 4]} ; Lischka, Hans ^{[3, 5, 2]} ; Machado, Francisco B. C. ^[1]

Afiliação do(s) autor(es)

^[1] Inst Tecnol Aeronaut, Dept Quim, 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 Chem & Biochem, Lubbock, TX 79409 - USA

^[4] Univ Nat Resources & Life Sci Vienna, Inst Soil Res, Peter Jordan Str 82, A-1190 Vienna - Austria

^[5] Univ Vienna, Inst Theoret Chem, A-1090 Vienna - Austria

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry A; v. 122, n. 49, p. 9464-9473, DEC 13 2018.
• Citações Web of Science: 1

Resumo

Aromaticity is a multivariable concept in organic chemistry that plays a central role for understanding the structure, stability, and reactivity of polycyclic aromatic hydrocarbons (PAHs). Several types of PAHs are characterized as singlet biradicaloid species and their chemical stability is intimately linked to the degree of aromatic character. In this study, theoretically designed routes to tune the biradical character (and thereby its chemical stability) of nitrogen-substituted octacenes have been investigated on the basis of the high-level multireference averaged quadratic coupled-cluster MR-AQCC method necessary for the appropriate description of polyradicaloid systems. The influence of nitrogen centers on the aromaticity of octacene is probed through structural (HOMA) and electron localization (ELF) indices by comparing the N- against NH-doping cases. These analyses reveal that the aromaticity and biradical character of octacene is only slightly affected by replacing one pair of CH groups with N atoms, i.e., by N-doping. However, a significant aromatic stabilization can be obtained when NH-doping is applied at the inner octacene rings; this is also accompanied by an overall decrease of the open-shell character, as evidenced by the gradual quenching of the unpaired electrons and increase in the singlet-triplet splittings when the NH doping groups are moved toward the center of the octacene molecule. Our findings aid in the rational design of new PAH compounds with balanced biradicaloid character and chemical stability which is important, e.g., for practical applications in organic solar cells based on the singlet fission mechanism. (AU)

• 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
• Processo FAPESP: 17/07707-3 - Estados excitados e natureza poliradicalar de poliacenos e periacenos
• Beneficiário: Francisco Bolivar Correto Machado
• Modalidade de apoio: Auxílio à Pesquisa - Regular