An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence

Yoshiaki Shoji; Yasuhiro Ikabata; Ivan Ryzhii; Rabia Ayub; Ouissam El Bakouri; Taiga Sato; Qi Wang; Tomoaki Miura; Buddhika S.B. Karunathilaka; Youichi Tsuchiya; Chihaya Adachi; Henrik Ottosson; Hiromi Nakai; Tadaaki Ikoma; Takanori Fukushima

doi:10.1002/anie.202106490

An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence

Yoshiaki Shoji, Yasuhiro Ikabata, Ivan Ryzhii, Rabia Ayub, Ouissam El Bakouri, Taiga Sato, Qi Wang, Tomoaki Miura, Buddhika S.B. Karunathilaka, Youichi Tsuchiya, Chihaya Adachi, Henrik Ottosson, Hiromi Nakai, Tadaaki Ikoma, Takanori Fukushima^*

^*Corresponding author for this work

School of Advanced Science and Engineering

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

9 Citations (Scopus)

Abstract

1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, Hückel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative. The crystal structure of the diazadiboretidine derivative revealed that the B₂N₂ ring adopts a planar rhombic geometry in the ground state. Yet, theoretical calculations showed that the B₂N₂ ring turns to a square geometry with a nonaromatic character in the lowest triplet state. Notably, the diazadiboretidine derivative has the lowest singlet and triplet states lying at close energy levels and displays blue phosphorescence.

Original language	English
Pages (from-to)	21817-21823
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	40
DOIs	https://doi.org/10.1002/anie.202106490
Publication status	Published - 2021 Sept 27

Keywords

DFT calculations
aromaticity
luminescence
main-group elements
reaction mechanisms

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.202106490

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Shoji, Y., Ikabata, Y., Ryzhii, I., Ayub, R., El Bakouri, O., Sato, T., Wang, Q., Miura, T., Karunathilaka, B. S. B., Tsuchiya, Y., Adachi, C., Ottosson, H., Nakai, H., Ikoma, T., & Fukushima, T. (2021). An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence. Angewandte Chemie - International Edition, 60(40), 21817-21823. https://doi.org/10.1002/anie.202106490

Shoji, Y, Ikabata, Y, Ryzhii, I, Ayub, R, El Bakouri, O, Sato, T, Wang, Q, Miura, T, Karunathilaka, BSB, Tsuchiya, Y, Adachi, C, Ottosson, H, Nakai, H, Ikoma, T & Fukushima, T 2021, 'An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence', Angewandte Chemie - International Edition, vol. 60, no. 40, pp. 21817-21823. https://doi.org/10.1002/anie.202106490

@article{54062d08c1584b8f9f4b21fbde28ca99,

title = "An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence",

abstract = "1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, H{\"u}ckel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative. The crystal structure of the diazadiboretidine derivative revealed that the B2N2 ring adopts a planar rhombic geometry in the ground state. Yet, theoretical calculations showed that the B2N2 ring turns to a square geometry with a nonaromatic character in the lowest triplet state. Notably, the diazadiboretidine derivative has the lowest singlet and triplet states lying at close energy levels and displays blue phosphorescence.",

keywords = "DFT calculations, aromaticity, luminescence, main-group elements, reaction mechanisms",

author = "Yoshiaki Shoji and Yasuhiro Ikabata and Ivan Ryzhii and Rabia Ayub and {El Bakouri}, Ouissam and Taiga Sato and Qi Wang and Tomoaki Miura and Karunathilaka, {Buddhika S.B.} and Youichi Tsuchiya and Chihaya Adachi and Henrik Ottosson and Hiromi Nakai and Tadaaki Ikoma and Takanori Fukushima",

note = "Funding Information: This work was supported by a Grant‐in‐Aid for Transformative Research Areas (A) “Condensed Conjugation” (JSPS KAKENHI Grant Numbers JP20H05868 for T.F. and JP20H05869 for Y.S.) from MEXT, JSPS KAKENHI (Grant Numbers JP19K22165 and JP20H02722 for Y.S.), the Research Program of “Five‐star Alliance” in “NJRC Mater. & Dev.”, and the Swedish Research Council (Grant Number 2019–05618 for H.O.). We thank Materials Analysis Division, Open Facility Center, Tokyo Institute of Technology, for their support with the NMR measurements. Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, and National Institutes of Natural Sciences (NINS), while other calculations were performed by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC) in Link{\"o}ping, Sweden, partially funded by the Swedish Research Council through grant number 2016‐07213. Funding Information: This work was supported by a Grant-in-Aid for Transformative Research Areas (A) ?Condensed Conjugation? (JSPS KAKENHI Grant Numbers JP20H05868 for T.F. and JP20H05869 for Y.S.) from MEXT, JSPS KAKENHI (Grant Numbers JP19K22165 and JP20H02722 for Y.S.), the Research Program of ?Five-star Alliance? in ?NJRC Mater. & Dev.?, and the Swedish Research Council (Grant Number 2019?05618 for H.O.). We thank Materials Analysis Division, Open Facility Center, Tokyo Institute of Technology, for their support with the NMR measurements. Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, and National Institutes of Natural Sciences (NINS), while other calculations were performed by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC) in Link?ping, Sweden, partially funded by the Swedish Research Council through grant number 2016-07213. Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH.",

year = "2021",

month = sep,

day = "27",

doi = "10.1002/anie.202106490",

language = "English",

volume = "60",

pages = "21817--21823",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "40",

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TY - JOUR

T1 - An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence

AU - Shoji, Yoshiaki

AU - Ikabata, Yasuhiro

AU - Ryzhii, Ivan

AU - Ayub, Rabia

AU - El Bakouri, Ouissam

AU - Sato, Taiga

AU - Wang, Qi

AU - Miura, Tomoaki

AU - Karunathilaka, Buddhika S.B.

AU - Tsuchiya, Youichi

AU - Adachi, Chihaya

AU - Ottosson, Henrik

AU - Nakai, Hiromi

AU - Ikoma, Tadaaki

AU - Fukushima, Takanori

N1 - Funding Information: This work was supported by a Grant‐in‐Aid for Transformative Research Areas (A) “Condensed Conjugation” (JSPS KAKENHI Grant Numbers JP20H05868 for T.F. and JP20H05869 for Y.S.) from MEXT, JSPS KAKENHI (Grant Numbers JP19K22165 and JP20H02722 for Y.S.), the Research Program of “Five‐star Alliance” in “NJRC Mater. & Dev.”, and the Swedish Research Council (Grant Number 2019–05618 for H.O.). We thank Materials Analysis Division, Open Facility Center, Tokyo Institute of Technology, for their support with the NMR measurements. Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, and National Institutes of Natural Sciences (NINS), while other calculations were performed by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC) in Linköping, Sweden, partially funded by the Swedish Research Council through grant number 2016‐07213. Funding Information: This work was supported by a Grant-in-Aid for Transformative Research Areas (A) ?Condensed Conjugation? (JSPS KAKENHI Grant Numbers JP20H05868 for T.F. and JP20H05869 for Y.S.) from MEXT, JSPS KAKENHI (Grant Numbers JP19K22165 and JP20H02722 for Y.S.), the Research Program of ?Five-star Alliance? in ?NJRC Mater. & Dev.?, and the Swedish Research Council (Grant Number 2019?05618 for H.O.). We thank Materials Analysis Division, Open Facility Center, Tokyo Institute of Technology, for their support with the NMR measurements. Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, and National Institutes of Natural Sciences (NINS), while other calculations were performed by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC) in Link?ping, Sweden, partially funded by the Swedish Research Council through grant number 2016-07213. Publisher Copyright: © 2021 Wiley-VCH GmbH.

PY - 2021/9/27

Y1 - 2021/9/27

N2 - 1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, Hückel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative. The crystal structure of the diazadiboretidine derivative revealed that the B2N2 ring adopts a planar rhombic geometry in the ground state. Yet, theoretical calculations showed that the B2N2 ring turns to a square geometry with a nonaromatic character in the lowest triplet state. Notably, the diazadiboretidine derivative has the lowest singlet and triplet states lying at close energy levels and displays blue phosphorescence.

AB - 1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, Hückel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative. The crystal structure of the diazadiboretidine derivative revealed that the B2N2 ring adopts a planar rhombic geometry in the ground state. Yet, theoretical calculations showed that the B2N2 ring turns to a square geometry with a nonaromatic character in the lowest triplet state. Notably, the diazadiboretidine derivative has the lowest singlet and triplet states lying at close energy levels and displays blue phosphorescence.

KW - DFT calculations

KW - aromaticity

KW - luminescence

KW - main-group elements

KW - reaction mechanisms

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U2 - 10.1002/anie.202106490

DO - 10.1002/anie.202106490

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C2 - 34097333

AN - SCOPUS:85109628559

SN - 1433-7851

VL - 60

SP - 21817

EP - 21823

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 40

ER -

An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence

Abstract

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ASJC Scopus subject areas

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