Ab initio and first principles theoretical investigations of triplet–triplet fluorescence in trimethylenemethane biradicals. Issue 87 (5th September 2016)

• Record Type: Journal Article
• Authors: Matsui, Yasunori; Usui, Kosuke; Ikeda, Hiroshi; Irle, Stephan
• Is Part Of: RSC advances. Volume 6:Issue 87(2016)
• Page Start: 83668
• Page End: 83672
• Publication Date: 2016-09-05
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6ra16580j
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Theoretical studies on triplet–triplet (T1 → T0 ) fluorescence of the arylated trimethylenemethane (TMM) biradicals, 3 2˙˙, were carried out using post-Hartree–Fock ab initio and various first principles density functional theory methods. Abstract : Theoretical studies on triplet–triplet (T1 → T0 ) fluorescence of the arylated trimethylenemethane (TMM) biradicals, 3 2˙˙, were carried out using post-Hartree–Fock ab initio and various first principles density functional theory methods. Analysis of optimized geometries including bond alternations and spin distributions indicates that the triplet ground ( 3 2˙˙ ) and excited ( 3 2˙˙* ) states of these biradicals have aromatic and quinoidal characteristics, respectively. Inspection of their calculated electronic structures shows that, in comparison to 3 2˙˙, one of the spins in 3 2˙˙* is more delocalized onto arene-rings linked to the TMM framework.