| Texto completo | |
| Autor(es): |
Das, Anita
[1]
;
Pinheiro, Jr., Max
[2]
;
Machado, Francisco B. C.
[2]
;
Aquino, Adelia J. A.
[1, 3]
;
Lischka, Hans
[4, 1]
Número total de Autores: 5
|
| Afiliação do(s) autor(es): | [1] Tianjin Univ, Sch Pharmaceut Sci & Technol, Tianjin 300072 - Peoples R China
[2] Inst Tecnol Aeronaut, Dept Quim, BR-12228900 Sao Paulo - Brazil
[3] Univ Nat Resources & Life Sci Vienna, Inst Soil Res, Peter Jordan Str 82, A-1190 Vienna - Austria
[4] Univ Vienna, Inst Theoret Chem, A-1090 Vienna - Austria
Número total de Afiliações: 4
|
| Tipo de documento: | Artigo Científico |
| Fonte: | ChemPhysChem; v. 19, n. 19, p. 2492-2499, OCT 5 2018. |
| Citações Web of Science: | 3 |
| Resumo | |
Zethrenes are interesting polycyclic aromatic hydrocarbons (PAHs), which possess unique optoelectronic and magnetic properties because of their singlet open-shell biradicaloid character, making them promising candidates for application in organic electronics. Tuning their properties is a key task in order to develop efficient compounds for practical use by balancing the desired biradicaloid character against its chemical instability. In this work, high-level theoretical multireference methods appropriate for the correct description of polyradicaloid systems are used to develop rules for doping of zethrenes by means of nitrogen taking heptazethrene (HZ) as a benchmark example. The results of the quantum chemical calculations have been concentrated on a series of quantitative descriptors such as unpaired densities and singlet-triplet (S-T) splittings. They clearly indicate different regions in the HZ where N-doping can either lead to strong enhancement of the biradicaloid character or to strong quenching towards a closed shell state. A wide scale of varying open-shell character is accessible from the different doping positions. It is shown that the S-T splittings correlate well with the total number of unpaired electrons in the medium range of biradicaloid character. For pronounced biradical character the S-T splitting decays to about zero with a margin of +/- 0.15eV. In the opposite closed-shell limit, much larger S-T splittings of up to 3eV are computed. (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 |