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 language | English |
|---|---|
| Pages (from-to) | 11410-11420 |
| Number of pages | 11 |
| Journal | Chemistry - A European Journal |
| Volume | 20 |
| Issue number | 36 |
| DOIs | |
| Publication status | Published - 2014 Jan 1 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Organic Chemistry
Cite this
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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 journal › Article
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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U2 - 10.1002/chem.201402831
DO - 10.1002/chem.201402831
M3 - Article
AN - SCOPUS:84906240042
VL - 20
SP - 11410
EP - 11420
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 36
ER -