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

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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

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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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, R. W., Huang, K. W., 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, 20(36), 11410-11420. https://doi.org/10.1002/chem.201402831