Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical properties

Xueliang Shi, Paula Mayorga Burrezo, Sangsu Lee, Wenhua Zhang, Bin Zheng, Gaole Dai, Jingjing Chang, Juan T. López Navarrete, Kuo Wei Huang, Dongho Kim, Juan Casado, Chunyan Chi

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

Recent studies demonstrated that aromaticity and biradical character play important roles in determining the ground-state structures and physical properties of quinoidal polycyclic hydrocarbons and oligothiophenes, a kind of molecular materials showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α-oligothiophenes with two indene units. The obtained molecules can be regarded as antiaromatic systems containing 4n π electrons with small singlet biradical character (y0). Their ground-state geometry and electronic structures were studied by X-ray crystallographic analysis, NMR, ESR and Raman spectroscopy, assisted by density functional theory calculations. With extension of the chain length, the molecules showed a gradual increase of the singlet biradical character accompanied by decreased antiaromaticity, finally leading to a highly reactive bisindeno[4]thienoacene (S4-TIPS) which has a singlet biradical ground state (y0= 0.202). Their optical and electronic properties in the neutral and charged states were systematically investigated by one-photon absorption, two-photon absorption, transient absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry, which could be correlated to the chain length dependent antiaromaticity and biradical character. Our detailed studies revealed a clear structure-aromaticity-biradical character-physical properties-reactivity relationship, which is of importance for tailored material design in the future. This journal is

Original languageEnglish
Pages (from-to)4490-4503
Number of pages14
JournalChemical Science
Volume5
Issue number11
DOIs
Publication statusPublished - 2014 Nov 1

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Chain length
Ground state
Physical properties
Cyclic Hydrocarbons
Photons
Spectroelectrochemistry
Magnetoelectronics
Molecules
Hybrid systems
Absorption spectroscopy
Electronic properties
Photonics
Cyclic voltammetry
Electronic structure
Density functional theory
Paramagnetic resonance
Raman spectroscopy
Electronic equipment
Optical properties
Nuclear magnetic resonance

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Shi, Xueliang ; Burrezo, Paula Mayorga ; Lee, Sangsu ; Zhang, Wenhua ; Zheng, Bin ; Dai, Gaole ; Chang, Jingjing ; López Navarrete, Juan T. ; Huang, Kuo Wei ; Kim, Dongho ; Casado, Juan ; Chi, Chunyan. / Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters : Syntheses, structures and chain length dependent physical properties. In: Chemical Science. 2014 ; Vol. 5, No. 11. pp. 4490-4503.
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abstract = "Recent studies demonstrated that aromaticity and biradical character play important roles in determining the ground-state structures and physical properties of quinoidal polycyclic hydrocarbons and oligothiophenes, a kind of molecular materials showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α-oligothiophenes with two indene units. The obtained molecules can be regarded as antiaromatic systems containing 4n π electrons with small singlet biradical character (y0). Their ground-state geometry and electronic structures were studied by X-ray crystallographic analysis, NMR, ESR and Raman spectroscopy, assisted by density functional theory calculations. With extension of the chain length, the molecules showed a gradual increase of the singlet biradical character accompanied by decreased antiaromaticity, finally leading to a highly reactive bisindeno[4]thienoacene (S4-TIPS) which has a singlet biradical ground state (y0= 0.202). Their optical and electronic properties in the neutral and charged states were systematically investigated by one-photon absorption, two-photon absorption, transient absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry, which could be correlated to the chain length dependent antiaromaticity and biradical character. Our detailed studies revealed a clear structure-aromaticity-biradical character-physical properties-reactivity relationship, which is of importance for tailored material design in the future. This journal is",
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Shi, X, Burrezo, PM, Lee, S, Zhang, W, Zheng, B, Dai, G, Chang, J, López Navarrete, JT, Huang, KW, Kim, D, Casado, J & Chi, C 2014, 'Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical properties', Chemical Science, vol. 5, no. 11, pp. 4490-4503. https://doi.org/10.1039/c4sc01769b

Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters : Syntheses, structures and chain length dependent physical properties. / Shi, Xueliang; Burrezo, Paula Mayorga; Lee, Sangsu; Zhang, Wenhua; Zheng, Bin; Dai, Gaole; Chang, Jingjing; López Navarrete, Juan T.; Huang, Kuo Wei; Kim, Dongho; Casado, Juan; Chi, Chunyan.

In: Chemical Science, Vol. 5, No. 11, 01.11.2014, p. 4490-4503.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters

T2 - Syntheses, structures and chain length dependent physical properties

AU - Shi, Xueliang

AU - Burrezo, Paula Mayorga

AU - Lee, Sangsu

AU - Zhang, Wenhua

AU - Zheng, Bin

AU - Dai, Gaole

AU - Chang, Jingjing

AU - López Navarrete, Juan T.

AU - Huang, Kuo Wei

AU - Kim, Dongho

AU - Casado, Juan

AU - Chi, Chunyan

PY - 2014/11/1

Y1 - 2014/11/1

N2 - Recent studies demonstrated that aromaticity and biradical character play important roles in determining the ground-state structures and physical properties of quinoidal polycyclic hydrocarbons and oligothiophenes, a kind of molecular materials showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α-oligothiophenes with two indene units. The obtained molecules can be regarded as antiaromatic systems containing 4n π electrons with small singlet biradical character (y0). Their ground-state geometry and electronic structures were studied by X-ray crystallographic analysis, NMR, ESR and Raman spectroscopy, assisted by density functional theory calculations. With extension of the chain length, the molecules showed a gradual increase of the singlet biradical character accompanied by decreased antiaromaticity, finally leading to a highly reactive bisindeno[4]thienoacene (S4-TIPS) which has a singlet biradical ground state (y0= 0.202). Their optical and electronic properties in the neutral and charged states were systematically investigated by one-photon absorption, two-photon absorption, transient absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry, which could be correlated to the chain length dependent antiaromaticity and biradical character. Our detailed studies revealed a clear structure-aromaticity-biradical character-physical properties-reactivity relationship, which is of importance for tailored material design in the future. This journal is

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