Inducing Curvature to Pyracylene upon π‐Expansion
John Bergner, Christian Walla, Frank Röminger, Andreas Dreuw, Milan Kivala
Abstract
We disclose a successive π-expansion of pyracylene towards boat-shaped polycyclic scaffolds. The unique structural features of the resulting compounds were revealed by X-ray crystallographic analysis. Depending on the extent of π-expansion the compounds display intense bathochromically shifted absorption bands in their UV/Vis spectra and are prone to several redox events as documented by cyclic voltammetry. The experimental observations are in line with the computational studies based on density functional theory, suggesting progressive narrowing of the HOMO-LUMO gap and distinct evolution of the electronic structure and aromaticity.
Topics & Concepts
Cyclic voltammetryCurvatureDensity functional theoryAromaticityHOMO/LUMORedoxElectronic structureNegative curvatureAbsorption (acoustics)Absorption spectroscopySpectral lineMaterials scienceCrystallographyComputational chemistryChemistryChemical physicsPhysicsGeometryMoleculeOpticsInorganic chemistryPhysical chemistryElectrodeMathematicsElectrochemistryOrganic chemistryQuantum mechanicsComposite materialSynthesis and Properties of Aromatic CompoundsLuminescence and Fluorescent MaterialsPhotochromic and Fluorescence Chemistry