Access to Functionalized Pyrenes, Peropyrenes, Terropyrenes, and Quarterropyrenes via Reductive Aromatization.
Simon WernerTobias VollgraffJörg SundermeyerPublished in: Angewandte Chemie (International ed. in English) (2021)
Herein we report a versatile concept for the synthesis of fourfold functionalized, soluble pyrenes, peropyrenes, terropyrenes, and quarterropyrenes. They were obtained by a modular stepwise approach towards the rylene scaffold via Suzuki-Miyaura cross coupling, oxidative cyclodehydrogenation in the presence of caesium hydroxide under air, and finally zinc-mediated reductive silylation. The silylated reaction products were characterized by X-ray crystallography. The first example of a synthesized and crystallized quarterropyrene is presented and its oxidation reaction investigated. The functionalized ropyrenes were systematically characterized by means of UV/Vis-NIR and photoluminescence spectroscopy showing a bathochromic shift of 80 nm per naphthalene unit and a nearly linear increase of the extinction coefficients. Cyclic voltammograms and DFT calculations identify them as electron-rich dyes and show a narrowing of the electrochemically determined HOMO-LUMO gap and lower oxidation potentials for the higher homologues.
Keyphrases
- quantum dots
- electron transfer
- density functional theory
- photodynamic therapy
- high resolution
- molecularly imprinted
- aqueous solution
- hydrogen peroxide
- oxide nanoparticles
- molecular dynamics
- single molecule
- magnetic resonance imaging
- molecular docking
- electron microscopy
- drug delivery
- tissue engineering
- computed tomography
- dual energy
- monte carlo
- high speed
- crystal structure
- simultaneous determination