Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical properties

Soumyajit Das, Sangsu Lee, Minjung Son, Xiaojian Zhu, Wenhua Zhang, Bin Zheng, Pan Hu, Zebing Zeng, Zhe Sun, Wangdong Zeng, Run Wei Li, Kuo Wei Huang, Jun Ding, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcalmol-1), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds. A matter of fusion mode! Fusion of a para-quinodimethane (p-QDM) subunit at the peri and β positions of perylene dimers leads to systems with different ground states, that is, open and closed shell (see picture). These systems showed large two-photon absorption cross sections and ultrafast excited-state dynamics relative to their corresponding pericondensed aromatic quaterrylene counterparts.

Original languageEnglish
Pages (from-to)11410-11420
Number of pages11
JournalChemistry - A European Journal
Volume20
Issue number36
DOIs
Publication statusPublished - 2014 Jan 1

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Perylene
Dimers
Ground state
Fusion reactions
Physical properties
Cyclic Hydrocarbons
Excited states
Energy gap
Photons
Hydrocarbons
Discrete Fourier transforms
Electronic properties
Electronic structure
Charge transfer
Derivatives
Experiments

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Das, Soumyajit ; Lee, Sangsu ; Son, Minjung ; Zhu, Xiaojian ; Zhang, Wenhua ; Zheng, Bin ; Hu, Pan ; Zeng, Zebing ; Sun, Zhe ; Zeng, Wangdong ; Li, Run Wei ; Huang, Kuo Wei ; Ding, Jun ; Kim, Dongho ; Wu, Jishan. / Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes : The effect of the fusion mode on the ground states and physical properties. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 36. pp. 11410-11420.
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title = "Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical properties",
abstract = "Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcalmol-1), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds. A matter of fusion mode! Fusion of a para-quinodimethane (p-QDM) subunit at the peri and β positions of perylene dimers leads to systems with different ground states, that is, open and closed shell (see picture). These systems showed large two-photon absorption cross sections and ultrafast excited-state dynamics relative to their corresponding pericondensed aromatic quaterrylene counterparts.",
author = "Soumyajit Das and Sangsu Lee and Minjung Son and Xiaojian Zhu and Wenhua Zhang and Bin Zheng and Pan Hu and Zebing Zeng and Zhe Sun and Wangdong Zeng and Li, {Run Wei} and Huang, {Kuo Wei} and Jun Ding and Dongho Kim and Jishan Wu",
year = "2014",
month = "1",
day = "1",
doi = "10.1002/chem.201402831",
language = "English",
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Das, S, Lee, S, Son, M, Zhu, X, Zhang, W, Zheng, B, Hu, P, Zeng, Z, Sun, Z, Zeng, W, Li, RW, Huang, KW, Ding, J, Kim, D & Wu, J 2014, 'Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical properties', Chemistry - A European Journal, vol. 20, no. 36, pp. 11410-11420. https://doi.org/10.1002/chem.201402831

Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes : The effect of the fusion mode on the ground states and physical properties. / Das, Soumyajit; Lee, Sangsu; Son, Minjung; Zhu, Xiaojian; Zhang, Wenhua; Zheng, Bin; Hu, Pan; Zeng, Zebing; Sun, Zhe; Zeng, Wangdong; Li, Run Wei; Huang, Kuo Wei; Ding, Jun; Kim, Dongho; Wu, Jishan.

In: Chemistry - A European Journal, Vol. 20, No. 36, 01.01.2014, p. 11410-11420.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes

T2 - The effect of the fusion mode on the ground states and physical properties

AU - Das, Soumyajit

AU - Lee, Sangsu

AU - Son, Minjung

AU - Zhu, Xiaojian

AU - Zhang, Wenhua

AU - Zheng, Bin

AU - Hu, Pan

AU - Zeng, Zebing

AU - Sun, Zhe

AU - Zeng, Wangdong

AU - Li, Run Wei

AU - Huang, Kuo Wei

AU - Ding, Jun

AU - Kim, Dongho

AU - Wu, Jishan

PY - 2014/1/1

Y1 - 2014/1/1

N2 - Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcalmol-1), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds. A matter of fusion mode! Fusion of a para-quinodimethane (p-QDM) subunit at the peri and β positions of perylene dimers leads to systems with different ground states, that is, open and closed shell (see picture). These systems showed large two-photon absorption cross sections and ultrafast excited-state dynamics relative to their corresponding pericondensed aromatic quaterrylene counterparts.

AB - Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcalmol-1), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds. A matter of fusion mode! Fusion of a para-quinodimethane (p-QDM) subunit at the peri and β positions of perylene dimers leads to systems with different ground states, that is, open and closed shell (see picture). These systems showed large two-photon absorption cross sections and ultrafast excited-state dynamics relative to their corresponding pericondensed aromatic quaterrylene counterparts.

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