Synergetic Role of Conformational Flexibility and Electronic Coupling for Quantitative Intramolecular Singlet Fission

Shunta Nakamura; Hayato Sakai; Hiroki Nagashima; Masaaki Fuki; Kakeru Onishi; Ramsha Khan; Yasuhiro Kobori; Nikolai V. Tkachenko; Taku Hasobe

doi:10.1021/acs.jpcc.1c04734

Synergetic Role of Conformational Flexibility and Electronic Coupling for Quantitative Intramolecular Singlet Fission

Shunta Nakamura, Hayato Sakai, Hiroki Nagashima, Masaaki Fuki, Kakeru Onishi, Ramsha Khan, Yasuhiro Kobori, Nikolai V. Tkachenko, Taku Hasobe

Materials Science and Environmental Engineering

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

22 Citations (Scopus)

Abstract

We present a novel design concept of molecular dimers for quantitative individual triplet yield (φΤ) through intramolecular singlet fission. We synthesized a series of tetracene (Tc) dimers bridged by different phenylene-based linkers, focusing on the conformational flexibility in addition to the electronic coupling. In transient absorption measurements, a 4,4′-biphenyl-bridged Tc dimer with weaker electronic coupling and larger conformational flexibility exhibited the quantitative φΤ: 196 ± 12% at high excitation energy. Moreover, decoupled spins associated with conformational change were directly characterized by time-resolved electron paramagnetic resonance. Strong interplay of the geometry change and electronic localization was revealed on the triplet pair dissociation through magnitudes of spin-spin exchange couplings. Thus, a synergetic role of conformational flexibility and electronic coupling in quantitative φΤ was clarified.

Original language	English
Pages (from-to)	18287-18296
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	125
Issue number	33
DOIs	https://doi.org/10.1021/acs.jpcc.1c04734
Publication status	Published - 2021
Publication type	A1 Journal article-refereed

Publication forum classification

Publication forum level 2

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

Access to Document

10.1021/acs.jpcc.1c04734

Chemistry Labs for optical spectroscopy, analysis, and synthesis
Ruoko, T.-P. (Contact) & Efimov, A. (Contact)
Materials Science and Environmental Engineering
Facility/equipment: Facility

Cite this

@article{73aad59a6ca4458292e73766cc525be3,

title = "Synergetic Role of Conformational Flexibility and Electronic Coupling for Quantitative Intramolecular Singlet Fission",

abstract = "We present a novel design concept of molecular dimers for quantitative individual triplet yield (φΤ) through intramolecular singlet fission. We synthesized a series of tetracene (Tc) dimers bridged by different phenylene-based linkers, focusing on the conformational flexibility in addition to the electronic coupling. In transient absorption measurements, a 4,4′-biphenyl-bridged Tc dimer with weaker electronic coupling and larger conformational flexibility exhibited the quantitative φΤ: 196 ± 12% at high excitation energy. Moreover, decoupled spins associated with conformational change were directly characterized by time-resolved electron paramagnetic resonance. Strong interplay of the geometry change and electronic localization was revealed on the triplet pair dissociation through magnitudes of spin-spin exchange couplings. Thus, a synergetic role of conformational flexibility and electronic coupling in quantitative φΤ was clarified.",

author = "Shunta Nakamura and Hayato Sakai and Hiroki Nagashima and Masaaki Fuki and Kakeru Onishi and Ramsha Khan and Yasuhiro Kobori and Tkachenko, {Nikolai V.} and Taku Hasobe",

note = "Funding Information: This work was partially supported by JSPS KAKENHI grant numbers of JP19H00888 and JP20K21174 and Grant-in-Aid for Transformative Research Areas, “Dynamic Exciton” (JP20H05832) to Y.K. and by JSPS KAKENHI grant nos. JP18H01957, JP18K19063, JP20H05234, JP20KK0120, JP21H01908, and JP21K19011 to T.H., JP20K05652 to H.S., and JP20J13133 to S.N. JP19K15506 to H.N. R.K. acknowledges Doctoral program of Tampere University for financial support. We are grateful to Dr. Tatsuo Nakagawa and Hiroaki Hanada (Unisoku Co., Ltd.) for picosecond transient absorption measurements by the Randomly Interleaved Pulse Train Method. This work was partially carried out by the joint research program of Molecular Photoscience Research Center, Kobe University, and the Research Program of “Five-star Alliance” in “NJRC Mater. & Dev.” Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

doi = "10.1021/acs.jpcc.1c04734",

language = "English",

volume = "125",

pages = "18287--18296",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "33",

}

TY - JOUR

T1 - Synergetic Role of Conformational Flexibility and Electronic Coupling for Quantitative Intramolecular Singlet Fission

AU - Nakamura, Shunta

AU - Sakai, Hayato

AU - Nagashima, Hiroki

AU - Fuki, Masaaki

AU - Onishi, Kakeru

AU - Khan, Ramsha

AU - Kobori, Yasuhiro

AU - Tkachenko, Nikolai V.

AU - Hasobe, Taku

N1 - Funding Information: This work was partially supported by JSPS KAKENHI grant numbers of JP19H00888 and JP20K21174 and Grant-in-Aid for Transformative Research Areas, “Dynamic Exciton” (JP20H05832) to Y.K. and by JSPS KAKENHI grant nos. JP18H01957, JP18K19063, JP20H05234, JP20KK0120, JP21H01908, and JP21K19011 to T.H., JP20K05652 to H.S., and JP20J13133 to S.N. JP19K15506 to H.N. R.K. acknowledges Doctoral program of Tampere University for financial support. We are grateful to Dr. Tatsuo Nakagawa and Hiroaki Hanada (Unisoku Co., Ltd.) for picosecond transient absorption measurements by the Randomly Interleaved Pulse Train Method. This work was partially carried out by the joint research program of Molecular Photoscience Research Center, Kobe University, and the Research Program of “Five-star Alliance” in “NJRC Mater. & Dev.” Publisher Copyright: © 2021 American Chemical Society.

PY - 2021

Y1 - 2021

N2 - We present a novel design concept of molecular dimers for quantitative individual triplet yield (φΤ) through intramolecular singlet fission. We synthesized a series of tetracene (Tc) dimers bridged by different phenylene-based linkers, focusing on the conformational flexibility in addition to the electronic coupling. In transient absorption measurements, a 4,4′-biphenyl-bridged Tc dimer with weaker electronic coupling and larger conformational flexibility exhibited the quantitative φΤ: 196 ± 12% at high excitation energy. Moreover, decoupled spins associated with conformational change were directly characterized by time-resolved electron paramagnetic resonance. Strong interplay of the geometry change and electronic localization was revealed on the triplet pair dissociation through magnitudes of spin-spin exchange couplings. Thus, a synergetic role of conformational flexibility and electronic coupling in quantitative φΤ was clarified.

AB - We present a novel design concept of molecular dimers for quantitative individual triplet yield (φΤ) through intramolecular singlet fission. We synthesized a series of tetracene (Tc) dimers bridged by different phenylene-based linkers, focusing on the conformational flexibility in addition to the electronic coupling. In transient absorption measurements, a 4,4′-biphenyl-bridged Tc dimer with weaker electronic coupling and larger conformational flexibility exhibited the quantitative φΤ: 196 ± 12% at high excitation energy. Moreover, decoupled spins associated with conformational change were directly characterized by time-resolved electron paramagnetic resonance. Strong interplay of the geometry change and electronic localization was revealed on the triplet pair dissociation through magnitudes of spin-spin exchange couplings. Thus, a synergetic role of conformational flexibility and electronic coupling in quantitative φΤ was clarified.

U2 - 10.1021/acs.jpcc.1c04734

DO - 10.1021/acs.jpcc.1c04734

M3 - Article

AN - SCOPUS:85114009615

SN - 1932-7447

VL - 125

SP - 18287

EP - 18296

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 33

ER -

Synergetic Role of Conformational Flexibility and Electronic Coupling for Quantitative Intramolecular Singlet Fission

Abstract

Publication forum classification

ASJC Scopus subject areas

Access to Document

Fingerprint

Equipment

Chemistry Labs for optical spectroscopy, analysis, and synthesis

Cite this