Push-Pull Type Oligo(N -annulated perylene)quinodimethanes: Chain Length and Solvent-Dependent Ground States and Physical Properties

Zebing Zeng, Sangsu Lee, Minjung Son, Kotaro Fukuda, Paula Mayorga Burrezo, Xiaojian Zhu, Qingbiao Qi, Run Wei Li, Juan T.López Navarrete, Jun Ding, Juan Casado, Masayoshi Nakano, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticle

60 Citations (Scopus)

Abstract

Research on stable open-shell singlet diradicaloids recently became a hot topic because of their unique optical, electronic, and magnetic properties and promising applications in materials science. So far, most reported singlet diradicaloid molecules have a symmetric structure, while asymmetric diradicaloids with an additional contribution of a dipolar zwitterionic form to the ground state were rarely studied. In this Article, a series of new push-pull type oligo(N-annulated perylene)quinodimethanes were synthesized. Their chain length and solvent-dependent ground states and physical properties were systematically investigated by various experimental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device, Raman spectroscopy, and electrochemistry. It was found that with extension of the chain length, the diradical character increases while the contribution of the zwitterionic form to the ground state becomes smaller. Because of the intramolecular charge transfer character, the physical properties of this push-pull system showed solvent dependence. In addition, density functional theory calculations on the diradical character and Hirshfeld charge were conducted to understand the chain length and solvent dependence of both symmetric and asymmetric systems. Our studies provided a comprehensive understanding on the fundamental structure- and environment-property relationships in the new asymmetric diradicaloid systems.

Original languageEnglish
Pages (from-to)8572-8583
Number of pages12
JournalJournal of the American Chemical Society
Volume137
Issue number26
DOIs
Publication statusPublished - 2015 Jul 8

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Perylene
Chain length
Ground state
Physical properties
Electrochemistry
Raman Spectrum Analysis
SQUIDs
Electron Spin Resonance Spectroscopy
X ray absorption
Materials science
Photons
Electronic properties
Density functional theory
Paramagnetic resonance
Raman spectroscopy
Charge transfer
Magnetic properties
Optical properties
X-Rays
Equipment and Supplies

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Zeng, Zebing ; Lee, Sangsu ; Son, Minjung ; Fukuda, Kotaro ; Burrezo, Paula Mayorga ; Zhu, Xiaojian ; Qi, Qingbiao ; Li, Run Wei ; Navarrete, Juan T.López ; Ding, Jun ; Casado, Juan ; Nakano, Masayoshi ; Kim, Dongho ; Wu, Jishan. / Push-Pull Type Oligo(N -annulated perylene)quinodimethanes : Chain Length and Solvent-Dependent Ground States and Physical Properties. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 26. pp. 8572-8583.
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abstract = "Research on stable open-shell singlet diradicaloids recently became a hot topic because of their unique optical, electronic, and magnetic properties and promising applications in materials science. So far, most reported singlet diradicaloid molecules have a symmetric structure, while asymmetric diradicaloids with an additional contribution of a dipolar zwitterionic form to the ground state were rarely studied. In this Article, a series of new push-pull type oligo(N-annulated perylene)quinodimethanes were synthesized. Their chain length and solvent-dependent ground states and physical properties were systematically investigated by various experimental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device, Raman spectroscopy, and electrochemistry. It was found that with extension of the chain length, the diradical character increases while the contribution of the zwitterionic form to the ground state becomes smaller. Because of the intramolecular charge transfer character, the physical properties of this push-pull system showed solvent dependence. In addition, density functional theory calculations on the diradical character and Hirshfeld charge were conducted to understand the chain length and solvent dependence of both symmetric and asymmetric systems. Our studies provided a comprehensive understanding on the fundamental structure- and environment-property relationships in the new asymmetric diradicaloid systems.",
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Zeng, Z, Lee, S, Son, M, Fukuda, K, Burrezo, PM, Zhu, X, Qi, Q, Li, RW, Navarrete, JTL, Ding, J, Casado, J, Nakano, M, Kim, D & Wu, J 2015, 'Push-Pull Type Oligo(N -annulated perylene)quinodimethanes: Chain Length and Solvent-Dependent Ground States and Physical Properties', Journal of the American Chemical Society, vol. 137, no. 26, pp. 8572-8583. https://doi.org/10.1021/jacs.5b04156

Push-Pull Type Oligo(N -annulated perylene)quinodimethanes : Chain Length and Solvent-Dependent Ground States and Physical Properties. / Zeng, Zebing; Lee, Sangsu; Son, Minjung; Fukuda, Kotaro; Burrezo, Paula Mayorga; Zhu, Xiaojian; Qi, Qingbiao; Li, Run Wei; Navarrete, Juan T.López; Ding, Jun; Casado, Juan; Nakano, Masayoshi; Kim, Dongho; Wu, Jishan.

In: Journal of the American Chemical Society, Vol. 137, No. 26, 08.07.2015, p. 8572-8583.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Push-Pull Type Oligo(N -annulated perylene)quinodimethanes

T2 - Chain Length and Solvent-Dependent Ground States and Physical Properties

AU - Zeng, Zebing

AU - Lee, Sangsu

AU - Son, Minjung

AU - Fukuda, Kotaro

AU - Burrezo, Paula Mayorga

AU - Zhu, Xiaojian

AU - Qi, Qingbiao

AU - Li, Run Wei

AU - Navarrete, Juan T.López

AU - Ding, Jun

AU - Casado, Juan

AU - Nakano, Masayoshi

AU - Kim, Dongho

AU - Wu, Jishan

PY - 2015/7/8

Y1 - 2015/7/8

N2 - Research on stable open-shell singlet diradicaloids recently became a hot topic because of their unique optical, electronic, and magnetic properties and promising applications in materials science. So far, most reported singlet diradicaloid molecules have a symmetric structure, while asymmetric diradicaloids with an additional contribution of a dipolar zwitterionic form to the ground state were rarely studied. In this Article, a series of new push-pull type oligo(N-annulated perylene)quinodimethanes were synthesized. Their chain length and solvent-dependent ground states and physical properties were systematically investigated by various experimental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device, Raman spectroscopy, and electrochemistry. It was found that with extension of the chain length, the diradical character increases while the contribution of the zwitterionic form to the ground state becomes smaller. Because of the intramolecular charge transfer character, the physical properties of this push-pull system showed solvent dependence. In addition, density functional theory calculations on the diradical character and Hirshfeld charge were conducted to understand the chain length and solvent dependence of both symmetric and asymmetric systems. Our studies provided a comprehensive understanding on the fundamental structure- and environment-property relationships in the new asymmetric diradicaloid systems.

AB - Research on stable open-shell singlet diradicaloids recently became a hot topic because of their unique optical, electronic, and magnetic properties and promising applications in materials science. So far, most reported singlet diradicaloid molecules have a symmetric structure, while asymmetric diradicaloids with an additional contribution of a dipolar zwitterionic form to the ground state were rarely studied. In this Article, a series of new push-pull type oligo(N-annulated perylene)quinodimethanes were synthesized. Their chain length and solvent-dependent ground states and physical properties were systematically investigated by various experimental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device, Raman spectroscopy, and electrochemistry. It was found that with extension of the chain length, the diradical character increases while the contribution of the zwitterionic form to the ground state becomes smaller. Because of the intramolecular charge transfer character, the physical properties of this push-pull system showed solvent dependence. In addition, density functional theory calculations on the diradical character and Hirshfeld charge were conducted to understand the chain length and solvent dependence of both symmetric and asymmetric systems. Our studies provided a comprehensive understanding on the fundamental structure- and environment-property relationships in the new asymmetric diradicaloid systems.

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