Enthalpy-Entropy Compensation Effect for Triplet Pair Dissociation of Intramolecular Singlet Fission in Phenylene Spacer-Bridged Hexacene Dimers

Shunta Nakamura; Hayato Sakai; Masaaki Fuki; Yasuhiro Kobori; Nikolai V. Tkachenko; Taku Hasobe

doi:10.1021/acs.jpclett.1c01430

Enthalpy-Entropy Compensation Effect for Triplet Pair Dissociation of Intramolecular Singlet Fission in Phenylene Spacer-Bridged Hexacene Dimers

Shunta Nakamura, Hayato Sakai, Masaaki Fuki, Yasuhiro Kobori, Nikolai V. Tkachenko, Taku Hasobe

Materiaalitiede ja ympäristötekniikka

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

13 Sitaatiot (Scopus)

10 Lataukset (Pure)

Abstrakti

Hexacene (Hc) is highly promising for singlet fission (SF). However, the number of SFs in Hc is extremely limited. As far as Hc dimers in solution are concerned, there is no report on the observation of the dissociation process from a correlated triplet pair (TT) to an individual one. The emphasis in this study is on the first observation of the quantitative TT generation together with the orientation-dependent photophysical discussions for TT dissociation usingpara- andmeta-phenyl-bridged Hc dimers. Moreover, the activation enthalpies of Hc dimers in TT dissociation are smaller than those of pentacene (Pc) dimers, whereas the relative entropic contributions for Gibbs free energy of activation are much larger than the enthalpic ones in both Hc and Pc dimers. This implies that the vibrational motions are responsible for the intramolecular conformation changes associated with the TT dissociation. Consequently, “enthalpy-entropy compensation” has a large impact on the rate constants and quantum yields.

Alkuperäiskieli	Englanti
Sivut	6457-6463
Sivumäärä	7
Julkaisu	Journal of Physical Chemistry Letters
Vuosikerta	12
Numero	28
DOI - pysyväislinkit	https://doi.org/10.1021/acs.jpclett.1c01430
Tila	Julkaistu - 22 heinäk. 2021
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

This work was partially supported by JSPS KAKENHI Grant Numbers 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, and JP21H01908 to T.H., JP20K05652 to H.S., and JP20J13133 to S.N. 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 3

!!ASJC Scopus subject areas

Yleinen materiaalitiede
Physical and Theoretical Chemistry

Pääsy asiakirjaan

10.1021/acs.jpclett.1c01430

enthalpy_entropy_compensation_effectAccepted author manuscript, 541 KBLisenssi: Unspecified

https://urn.fi/URN:NBN:fi:tuni-202201131295Lisenssi: Unspecified

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title = "Enthalpy-Entropy Compensation Effect for Triplet Pair Dissociation of Intramolecular Singlet Fission in Phenylene Spacer-Bridged Hexacene Dimers",

abstract = "Hexacene (Hc) is highly promising for singlet fission (SF). However, the number of SFs in Hc is extremely limited. As far as Hc dimers in solution are concerned, there is no report on the observation of the dissociation process from a correlated triplet pair (TT) to an individual one. The emphasis in this study is on the first observation of the quantitative TT generation together with the orientation-dependent photophysical discussions for TT dissociation usingpara- andmeta-phenyl-bridged Hc dimers. Moreover, the activation enthalpies of Hc dimers in TT dissociation are smaller than those of pentacene (Pc) dimers, whereas the relative entropic contributions for Gibbs free energy of activation are much larger than the enthalpic ones in both Hc and Pc dimers. This implies that the vibrational motions are responsible for the intramolecular conformation changes associated with the TT dissociation. Consequently, “enthalpy-entropy compensation” has a large impact on the rate constants and quantum yields.",

author = "Shunta Nakamura and Hayato Sakai and Masaaki Fuki and Yasuhiro Kobori and Tkachenko, {Nikolai V.} and Taku Hasobe",

note = "Funding Information: This work was partially supported by JSPS KAKENHI Grant Numbers 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, and JP21H01908 to T.H., JP20K05652 to H.S., and JP20J13133 to S.N. 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",

month = jul,

day = "22",

doi = "10.1021/acs.jpclett.1c01430",

language = "English",

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AU - Nakamura, Shunta

AU - Sakai, Hayato

AU - Fuki, Masaaki

AU - Kobori, Yasuhiro

AU - Tkachenko, Nikolai V.

AU - Hasobe, Taku

N1 - Funding Information: This work was partially supported by JSPS KAKENHI Grant Numbers 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, and JP21H01908 to T.H., JP20K05652 to H.S., and JP20J13133 to S.N. 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 - 2021/7/22

Y1 - 2021/7/22

N2 - Hexacene (Hc) is highly promising for singlet fission (SF). However, the number of SFs in Hc is extremely limited. As far as Hc dimers in solution are concerned, there is no report on the observation of the dissociation process from a correlated triplet pair (TT) to an individual one. The emphasis in this study is on the first observation of the quantitative TT generation together with the orientation-dependent photophysical discussions for TT dissociation usingpara- andmeta-phenyl-bridged Hc dimers. Moreover, the activation enthalpies of Hc dimers in TT dissociation are smaller than those of pentacene (Pc) dimers, whereas the relative entropic contributions for Gibbs free energy of activation are much larger than the enthalpic ones in both Hc and Pc dimers. This implies that the vibrational motions are responsible for the intramolecular conformation changes associated with the TT dissociation. Consequently, “enthalpy-entropy compensation” has a large impact on the rate constants and quantum yields.

AB - Hexacene (Hc) is highly promising for singlet fission (SF). However, the number of SFs in Hc is extremely limited. As far as Hc dimers in solution are concerned, there is no report on the observation of the dissociation process from a correlated triplet pair (TT) to an individual one. The emphasis in this study is on the first observation of the quantitative TT generation together with the orientation-dependent photophysical discussions for TT dissociation usingpara- andmeta-phenyl-bridged Hc dimers. Moreover, the activation enthalpies of Hc dimers in TT dissociation are smaller than those of pentacene (Pc) dimers, whereas the relative entropic contributions for Gibbs free energy of activation are much larger than the enthalpic ones in both Hc and Pc dimers. This implies that the vibrational motions are responsible for the intramolecular conformation changes associated with the TT dissociation. Consequently, “enthalpy-entropy compensation” has a large impact on the rate constants and quantum yields.

U2 - 10.1021/acs.jpclett.1c01430

DO - 10.1021/acs.jpclett.1c01430

M3 - Article

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SN - 1948-7185

VL - 12

SP - 6457

EP - 6463

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 28

ER -

Enthalpy-Entropy Compensation Effect for Triplet Pair Dissociation of Intramolecular Singlet Fission in Phenylene Spacer-Bridged Hexacene Dimers

Abstrakti

Rahoitus

Julkaisufoorumi-taso

!!ASJC Scopus subject areas

Pääsy asiakirjaan

Sormenjälki

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