RT Journal Article
T1 Monoradicals and diradicals of dibenzofluoreno[3,2-b]fluorene isomers: mechanisms of electronic delocalization
A1 Hayashi, Hideki
A1 Barker, Joshua E.
A1 Cárdenas Valdivia, Abel
A1 Kishi, Ryohei
A1 MacMillan, Samantha N.
A1 Gómez-García, Carlos J.
A1 Miyauchi, Hidenori
A1 Nakamura, Yosuke
A1 Nakano, Masayoshi
A1 Kato, Shin-ichiro
A1 Haley, Michael M.
A1 Casado-Cordón, Juan
K1 Radicales (Química)
K1 Reactividad (Química)
AB The preparation of a series of dibenzo- and tetrabenzo-fused fluoreno[3,2-b]fluorenes is disclosed, and the diradicaloid properties of these molecules are compared with those of a similar, previously reported series of anthracene-based diradicaloids. Insights on the diradical mode of delocalization tuning by constitutional isomerism of the external naphthalenes has been explored by means of the physical approach (dissection of the electronic properties in terms of electronic repulsion and transfer integral) of diradicals. This study has also been extended to the redox species of the two series of compounds and found that the radical cations have the same stabilization mode by delocalization that the neutral diradicals while the radical anions, contrarily, are stabilized by aromatization of the central core. The synthesis of the fluorenofluorene series and their characterization by electronic absorption and vibrational Raman spectroscopies, X-ray diffraction, SQUID measurements, electrochemistry, in situ UV-Vis-NIR absorption spectroelectrochemistry, and theoretical calculations is presented. This work attempts to unify the properties of different series of diradicaloids in a common argument as well as the properties of the carbocations and carbanions derived from them.
PB American Chemical Society
YR 2020
FD 2020-05-07
LK https://hdl.handle.net/10630/36567
UL https://hdl.handle.net/10630/36567
LA eng
NO Hideki Hayashi, Joshua E. Barker, Abel Cárdenas Valdivia, Ryohei Kishi, Samantha N. MacMillan, Carlos J. Gómez-García, Hidenori Miyauchi, Yosuke Nakamura, Masayoshi Nakano, Shin-ichiro Kato, Michael M. Haley, and Juan Casado Journal of the American Chemical Society 2020 142 (48), 20444-20455 DOI: 10.1021/jacs.0c09588
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 12 abr 2026