124582-37-2Relevant articles and documents
Colorless to purple-red switching electrochromic anthraquinone imides with broad visible/near-IR absorptions in the radical anion state: Simulation-aided molecular design
Chen, Fengkun,Zhang, Jie,Jiang, Hong,Wan, Xinhua
, p. 1497 - 1503 (2013)
The large redshift of near-infrared (NIR) absorptions of nitro-substituted anthraquinone imide (Nitro-AQI) radical anions, relative to other AQI derivatives, is rationalized based on quantum chemical calculations. Calculations reveal that the delocalization effects of electronegative substitution in the radical anion states is dramatically enhanced, thus leading to a significant decrease in the HOMO-LUMO band gap in the radical anion states. Based on this understanding, an AQI derivative with an even stronger electron-withdrawing dicyanovinyl (di-CN) substituent was designed and prepared. The resulting molecule, di-CN-AQI, displays no absorption in the Vis/NIR region in the neutral state, but absorbs intensively in the range of λ=700-1000 (λmax≈860 nm) and λ=1100-1800 nm (λmax≈1400 nm) upon one-electron reduction; this is accompanied by a transition from a highly transmissive colorless solution to one that is purple-red. The relationship between calculated radical anionic HOMO-LUMO gaps and the electron-withdrawing capacity of the substituents is also determined by employing Hammett parameter, which could serve as a theoretical tool for further molecular design.
From Acenaphthenes to (+)-Delavatine A: Visible-Light-Induced Ring Closure of Methyl (α-Naphthyl) Acrylates
Peez, Theodor,Luy, Jan-Niclas,Harms, Klaus,Tonner, Ralf,Koert, Ulrich
supporting information, p. 17686 - 17690 (2018/11/10)
Disclosed herein is a visible light mediated cyclization of methyl (α-naphthyl) acrylates and heteroaromatic analogues yielding substituted acenaphthenes and azaacenaphthenes. This highly functional-group-tolerant transformation was put to the test in an enantioselective formal synthesis of delavatine A. Mechanistic details were elucidated by DFT-calculations revealing an unusual intramolecular H-transfer mediated by a primary amine. The generality of this transformation enables a novel synthetic strategy of five membered ring annulation at an advanced stage, allowing reliance upon naphthalene chemistry up to the point of acenaphthene construction.
