title: Steric Enhancement of the Chemiluminescence of Luminols.
abstract: A surprising 20-fold increase in chemiluminescence efficiency was observed for dialkyl luminol derivatives in comparison with the parent compound. This effect could be a direct consequence of steric gearing which facilitates the transition from the intermediate endoperoxide to the electronically excited phthalate. Mechanistic aspects of this process have been supported by computational calculations (CASPT2//CASSCF).
authors.affiliation: Department of Chemistry, University of Cologne (Germany).
authors.forename: Axel G
authors.initials: AG
authors.lastname: Griesbeck
authors.affiliation: Department of Chemistry, University of Cologne (Germany).
authors.forename: Yrene
authors.initials: Y
authors.lastname: Díaz-Miara
authors.affiliation: Department of Chemistry, University of Cologne (Germany).
authors.forename: Robert
authors.initials: R
authors.lastname: Fichtler
authors.affiliation: Institute of Organic Chemistry, University of Regensburg, Universitaetstr. 31, 93040 Regensburg (Germany).
authors.forename: Axel
authors.initials: A
authors.lastname: Jacobi von Wangelin
authors.affiliation: Institute of Organic Chemistry, University of Regensburg, Universitaetstr. 31, 93040 Regensburg (Germany). raul.perez-ruiz@ur.de.
authors.forename: Raúl
authors.initials: R
authors.lastname: Pérez-Ruiz
authors.affiliation: Departamento de Química, Centro de Investigación en Síntesis, Química (CSIQ), Universidad de La Rioja, Madre de Dios, 51, 26006, Logroño (Spain). diego.sampedro@unirioja.es.
authors.forename: Diego
authors.initials: D
authors.lastname: Sampedro
mesh_terms: D000473:Alkanes / Q000737:chemistry; D049449:Luminescence; D008165:Luminol / Q000737:chemistry*; D008958:Models, Molecular; D010795:Phthalic Acids / Q000737:chemistry; D011789:Quantum Theory
chemical_list: D000473:Alkanes; D010795:Phthalic Acids; D008165:Luminol; C032279:phthalic acid
keywords: ab initio calculations; chemiluminescence; conical intersections; luminols; steric gearing