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

Materiaalitiede ja ympäristötekniikka

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

21 Sitaatiot (Scopus)

Abstrakti

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.

Alkuperäiskieli	Englanti
Sivut	18287-18296
Sivumäärä	10
Julkaisu	Journal of Physical Chemistry C
Vuosikerta	125
Numero	33
DOI - pysyväislinkit	https://doi.org/10.1021/acs.jpcc.1c04734
Tila	Julkaistu - 2021
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

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.”

Julkaisufoorumi-taso

Jufo-taso 2

!!ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Yleinen energiatiede
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

Pääsy asiakirjaan

10.1021/acs.jpcc.1c04734

Siteeraa tätä

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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 ACS",

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

Abstrakti

Rahoitus

Julkaisufoorumi-taso

!!ASJC Scopus subject areas

Pääsy asiakirjaan

Sormenjälki

Siteeraa tätä