The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers

Ryo Hayasaka; Hayato Sakai; Masaaki Fuki; Tsubasa Okamoto; Ramsha Khan; Masahiro Higashi; Nikolai V. Tkachenko; Yasuhiro Kobori; Taku Hasobe

doi:10.1002/anie.202315747

The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers

Ryo Hayasaka
, Hayato Sakai
, Masaaki Fuki
, Tsubasa Okamoto
, Ramsha Khan
, Masahiro Higashi
, Nikolai V. Tkachenko^*
, Yasuhiro Kobori^*
, Taku Hasobe^*

^*Tämän työn vastaava kirjoittaja

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

14 Sitaatiot (Scopus)

13 Lataukset (Pure)

Abstrakti

A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc−Ph(2,n)−(Pc)₂: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton (⁵TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)₂ has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)₂ exhibits a high-yield ⁵TT together with quantitative singlet TT (¹TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in ¹TT spin conversion of Fc−Ph(2,4)−(Pc)₂ is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in ¹TT is attributable to weakened metal-ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in ¹TT unpaired orbitals.

Alkuperäiskieli	Englanti
Artikkeli	e202315747
Julkaisu	Angewandte Chemie - International Edition
Vuosikerta	63
Numero	8
Varhainen verkossa julkaisun päivämäärä	5 tammik. 2024
DOI - pysyväislinkit	https://doi.org/10.1002/anie.202315747
Tila	Julkaistu - helmik. 2024
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

Thus, the quick spin relaxation after ISF in TT is revealed for reverse Q−S conversions to obtain the emissive spin polarization via the singlet deactivation. The present quick spin relaxation and conformation dynamics are very consistent with the large Δ in Table 2 causing the modulation of the spin‐spin interactions in Fc−Ph(2,4)−(Pc). This relaxation dynamics is supported by absence of spin echo signal by the pulsed EPR measurement (Figure S103). We also performed TREPR measurements of Xan−Ph(2,4)−(Pc) in toluene/paraffin mixture (1/9, v/v) at room temperature (Figure S104). The absorptive spin polarized spectra around 340 mT are very consistent with the data in Figure 8 observed in Fc−Ph(2,4)−(Pc) and with the center absorptive spin polarization of TT observed in our previous report in a dimer in toluene/paraffin mixture (1/9, v/v) at room temperature. S ≠ 2 2 2 5 [10b]

Rahoittajat	Rahoittajan numero
Molecular Photoscience Research Center, Kobe University
The Japan Society for the Promotion of Science (JSPS)	22H04558, JP20H05839, JP19H00888, JP21H05403, JP21K19011, JP20H05832, JPMJCR23I6, JP20KK0120, JP20H05234, JP23K04708, JP20K05652, JP21H01908, JP23H04876, JP20K21174

Julkaisufoorumi-taso

Jufo-taso 3

!!ASJC Scopus subject areas

Catalysis
Yleinen kemia

Pääsy asiakirjaan

10.1002/anie.202315747Lisenssi: CC BY

Angew Chem Int Ed - 2024 - Hayasaka - The Effect of Torsional Motion on Multiexciton Formation through IntramolecularFinal published version, 2,36 MBLisenssi: CC BY

https://urn.fi/URN:NBN:fi:tuni-202402202411Lisenssi: CC BY

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@article{ce6d874f03114ef4835add1f871bd43c,

title = "The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers",

abstract = "A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc−Ph(2,n)−(Pc)2: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton (5TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)2 exhibits a high-yield 5TT together with quantitative singlet TT (1TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1TT spin conversion of Fc−Ph(2,4)−(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1TT is attributable to weakened metal-ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1TT unpaired orbitals.",

keywords = "Ferrocene, Multiexciton Formation, Pentacene, Rotational Motion, Singlet Fission",

author = "Ryo Hayasaka and Hayato Sakai and Masaaki Fuki and Tsubasa Okamoto and Ramsha Khan and Masahiro Higashi and Tkachenko, \{Nikolai V.\} and Yasuhiro Kobori and Taku Hasobe",

note = "Publisher Copyright: {\textcopyright} 2024 Wiley-VCH GmbH.",

year = "2024",

month = feb,

doi = "10.1002/anie.202315747",

language = "English",

volume = "63",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley \& Sons",

number = "8",

}

TY - JOUR

T1 - The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers

AU - Hayasaka, Ryo

AU - Sakai, Hayato

AU - Fuki, Masaaki

AU - Okamoto, Tsubasa

AU - Khan, Ramsha

AU - Higashi, Masahiro

AU - Tkachenko, Nikolai V.

AU - Kobori, Yasuhiro

AU - Hasobe, Taku

PY - 2024/2

Y1 - 2024/2

N2 - A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc−Ph(2,n)−(Pc)2: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton (5TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)2 exhibits a high-yield 5TT together with quantitative singlet TT (1TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1TT spin conversion of Fc−Ph(2,4)−(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1TT is attributable to weakened metal-ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1TT unpaired orbitals.

AB - A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc−Ph(2,n)−(Pc)2: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton (5TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)2 exhibits a high-yield 5TT together with quantitative singlet TT (1TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1TT spin conversion of Fc−Ph(2,4)−(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1TT is attributable to weakened metal-ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1TT unpaired orbitals.

KW - Ferrocene

KW - Multiexciton Formation

KW - Pentacene

KW - Rotational Motion

KW - Singlet Fission

U2 - 10.1002/anie.202315747

DO - 10.1002/anie.202315747

M3 - Article

AN - SCOPUS:85182416754

SN - 1433-7851

VL - 63

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 8

M1 - e202315747

ER -

The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers

Abstrakti

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!!ASJC Scopus subject areas

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