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

Materials Science and Environmental Engineering

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6 Citations (Scopus)

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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.

Original language	English
Article number	e202315747
Journal	Angewandte Chemie - International Edition
Volume	63
Issue number	8
Early online date	5 Jan 2024
DOIs	https://doi.org/10.1002/anie.202315747
Publication status	Published - Feb 2024
Publication type	A1 Journal article-refereed

Keywords

Ferrocene
Multiexciton Formation
Pentacene
Rotational Motion
Singlet Fission

Publication forum classification

Publication forum level 3

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202315747Licence: CC BY

Angew Chem Int Ed - 2024 - Hayasaka - The Effect of Torsional Motion on Multiexciton Formation through IntramolecularFinal published version, 2.36 MBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202402202411Licence: 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",

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doi = "10.1002/anie.202315747",

language = "English",

volume = "63",

journal = "Angewandte Chemie - International Edition",

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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

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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

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DO - 10.1002/anie.202315747

M3 - Article

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ER -

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

Abstract

Keywords

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