Redox properties of non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons: The effect of peripheral pentagon annelation

Autor:	Leonardus W. Jenneskens, Carola Koper, Martin Sarobe
Přispěvatelé:	Fysisch-organische chemie van geordende systemen, Chemical Biology 1, Dep Scheikunde
Rok vydání:	2004
Předmět:	chemistry.chemical_classification Annulation Chemistry Stereochemistry General Physics and Astronomy Electron Redox Crystallography Hydrocarbon Electron affinity Molecule Physical and Theoretical Chemistry Cyclic voltammetry HOMO/LUMO
Zdroj:	Phys. Chem. Chem. Phys.. 6:319-327
ISSN:	1463-9084 1463-9076
Popis:	The redox properties of 23 alternant PAH and non-alternant mono- and bis-CP-PAH that contain annelated peripheral pentagons were determined using cyclic voltammetry. The results show that peripheral cyclopenta-fusion markedly enhances their electron affinity. Unexpectedly for the non-alternant PAH, a good linear correlation between the first reduction potential [E1/2(0/−1) V vs. SCE] and their standard Huckel LUMO energy (−eLUMO/β) is found. This indicates that the peripheral pentagons perturb the LUMO of the original alternant PAH core in a systematic fashion. A survey of the reduction behaviour of the mono- and bis-CP-PAH reveals that upon reduction the effect of the cyclopenta-moiety on the remainder of the molecule becomes negligible. Evidence for the formation of 6π-electron cyclopentadienide sub-structures is obtained, i.e. localization of the added electrons in the peripheral pentagons occurs.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::449ca115da0b90038c1fee215839f545 https://doi.org/10.1039/b312234d Zobrazit plný text záznamu