Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State

Ikuo Kawashima; Hiroaki Imoto; Masatoshi Ishida; Hiroyuki Furuta; Shunsuke Yamamoto; Masaya Mitsuishi; Susumu Tanaka; Toshiki Fujii; Kensuke Naka

doi:10.1002/anie.201904882

Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State

Ikuo Kawashima, Hiroaki Imoto, Masatoshi Ishida, Hiroyuki Furuta, Shunsuke Yamamoto, Masaya Mitsuishi, Susumu Tanaka, Toshiki Fujii, Kensuke Naka

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

Abstract

Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green-to-red region (500–700 nm) and the near-ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S₁) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S₁ states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S₁ states.

Original language	English
Pages (from-to)	11686-11690
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	34
DOIs	https://doi.org/10.1002/anie.201904882
Publication status	Published - 2019 Aug 19

Keywords

Baird's rule
aromaticity
arsepins
excited-state aromaticity

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201904882

Cite this

@article{40bce5e635a44203b5f5a9b1a276e06f,

title = "Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State",

abstract = "Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green-to-red region (500–700 nm) and the near-ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S1) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S1 states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S1 states.",

keywords = "Baird's rule, aromaticity, arsepins, excited-state aromaticity",

author = "Ikuo Kawashima and Hiroaki Imoto and Masatoshi Ishida and Hiroyuki Furuta and Shunsuke Yamamoto and Masaya Mitsuishi and Susumu Tanaka and Toshiki Fujii and Kensuke Naka",

note = "Funding Information: The work in Kyoto was supported by JSPS KAKENHI, grant number JP17H04577 (Coordination Asymmetry), to H.I. The work in Kyushu was supported by JSPS KAKENHI, grant numbers JP19H04586 and JP19K05439, to M.I. The work in Tohoku was supported by the Research Program of “Five-star Alliance” in “NJRC Mater. & Dev.” Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = aug,

day = "19",

doi = "10.1002/anie.201904882",

language = "English",

volume = "58",

pages = "11686--11690",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "34",

}

TY - JOUR

T1 - Dibenzoarsepins

T2 - Planarization of 8π-Electron System in the Lowest Singlet Excited State

AU - Kawashima, Ikuo

AU - Imoto, Hiroaki

AU - Ishida, Masatoshi

AU - Furuta, Hiroyuki

AU - Yamamoto, Shunsuke

AU - Mitsuishi, Masaya

AU - Tanaka, Susumu

AU - Fujii, Toshiki

AU - Naka, Kensuke

N1 - Funding Information: The work in Kyoto was supported by JSPS KAKENHI, grant number JP17H04577 (Coordination Asymmetry), to H.I. The work in Kyushu was supported by JSPS KAKENHI, grant numbers JP19H04586 and JP19K05439, to M.I. The work in Tohoku was supported by the Research Program of “Five-star Alliance” in “NJRC Mater. & Dev.” Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/8/19

Y1 - 2019/8/19

N2 - Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green-to-red region (500–700 nm) and the near-ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S1) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S1 states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S1 states.

AB - Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green-to-red region (500–700 nm) and the near-ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S1) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S1 states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S1 states.

KW - Baird's rule

KW - aromaticity

KW - arsepins

KW - excited-state aromaticity

UR - http://www.scopus.com/inward/record.url?scp=85069882380&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85069882380&partnerID=8YFLogxK

U2 - 10.1002/anie.201904882

DO - 10.1002/anie.201904882

M3 - Article

C2 - 31251829

AN - SCOPUS:85069882380

SN - 1433-7851

VL - 58

SP - 11686

EP - 11690

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 34

ER -

Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this