Ab initio and first principles theoretical investigations of triplet-triplet fluorescence in trimethylenemethane biradicals

Yasunori Matsui; Kosuke Usui; Hiroshi Ikeda; Stephan Irle

doi:10.1039/c6ra16580j

Ab initio and first principles theoretical investigations of triplet-triplet fluorescence in trimethylenemethane biradicals

Yasunori Matsui, Kosuke Usui, Hiroshi Ikeda, Stephan Irle

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3 Scopus citations

Abstract

Theoretical studies on triplet-triplet (T₁ → T₀) fluorescence of the arylated trimethylenemethane (TMM) biradicals, ³2, 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 (³2) and excited (³2∗) states of these biradicals have aromatic and quinoidal characteristics, respectively. Inspection of their calculated electronic structures shows that, in comparison to ³2, one of the spins in ³2∗ is more delocalized onto arene-rings linked to the TMM framework.

Original language	English
Pages (from-to)	83668-83672
Number of pages	5
Journal	RSC Advances
Volume	6
Issue number	87
DOIs	https://doi.org/10.1039/c6ra16580j
State	Published - 2016
Externally published	Yes

Funding

The authors acknowledge valuable discussions with Assistant Professor Daisuke Yokogawa in Nagoya University. This research was financially supported by A-STEP (No. AS231Z02594D) and ALCA (No. 1125217700) by Japan Science and Technology Agency (JST). K.U. appreciates support by the IGER program of Nagoya University. H. I. gratefully acknowledges financial support in the form of a Grant-in-Aid for Innovative Areas "π-Space" (No. 21108520 and 23108718 in the Area No. 2007) and "Stimuli-responsive Chemical Species" (No. 24109009 in the Area No. 2408), and the Scientific Research (B) (No. JP20044027 and JP23350023 in the Area No. 2408), and the Challenging Exploratory Research (No. JP21655016 and JP24655037) from JSPS, Japan. S. I. was partially supported by CREST grant from JST.

Funders	Funder number
Japan Society for the Promotion of Science
Japan Science and Technology Agency
Core Research for Evolutional Science and Technology
Nagoya University	21108520, 23108718, JP24655037, JP23350023, JP21655016, JP20044027, 24109009
Advanced Low Carbon Technology Research and Development Program	1125217700
Adaptable and Seamless Technology Transfer Program through Target-Driven R and D	AS231Z02594D

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title = "Ab initio and first principles theoretical investigations of triplet-triplet fluorescence in trimethylenemethane biradicals",

abstract = "Theoretical studies on triplet-triplet (T1 → T0) fluorescence of the arylated trimethylenemethane (TMM) biradicals, 32, 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 (32) and excited (32∗) states of these biradicals have aromatic and quinoidal characteristics, respectively. Inspection of their calculated electronic structures shows that, in comparison to 32, one of the spins in 32∗ is more delocalized onto arene-rings linked to the TMM framework.",

author = "Yasunori Matsui and Kosuke Usui and Hiroshi Ikeda and Stephan Irle",

note = "Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/c6ra16580j",

language = "English",

volume = "6",

pages = "83668--83672",

journal = "RSC Advances",

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T1 - Ab initio and first principles theoretical investigations of triplet-triplet fluorescence in trimethylenemethane biradicals

AU - Matsui, Yasunori

AU - Usui, Kosuke

AU - Ikeda, Hiroshi

AU - Irle, Stephan

PY - 2016

Y1 - 2016

N2 - Theoretical studies on triplet-triplet (T1 → T0) fluorescence of the arylated trimethylenemethane (TMM) biradicals, 32, 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 (32) and excited (32∗) states of these biradicals have aromatic and quinoidal characteristics, respectively. Inspection of their calculated electronic structures shows that, in comparison to 32, one of the spins in 32∗ is more delocalized onto arene-rings linked to the TMM framework.

AB - Theoretical studies on triplet-triplet (T1 → T0) fluorescence of the arylated trimethylenemethane (TMM) biradicals, 32, 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 (32) and excited (32∗) states of these biradicals have aromatic and quinoidal characteristics, respectively. Inspection of their calculated electronic structures shows that, in comparison to 32, one of the spins in 32∗ is more delocalized onto arene-rings linked to the TMM framework.

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DO - 10.1039/c6ra16580j

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JO - RSC Advances

JF - RSC Advances

IS - 87

ER -

Ab initio and first principles theoretical investigations of triplet-triplet fluorescence in trimethylenemethane biradicals

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