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Title: Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states

Abstract

A analysis of the electronic and molecular structures of new molecular materials based on zethrene is presented with particular attention to those systems having a central benzo-quinoidal core able to generate Kekulé biradicals whose stability is provided by the aromaticity recovery in this central unit. These Kekulé biradicals display singlet ground electronic states thanks to double spin polarization and have low-energy lying triplet excited states also featured by the aromaticity gain. Pro-aromatization is also the driving force for the stabilization of the ionized species. Moreover, the low energy lying singlet excited states also display a profound biradical fingerprint allowing to singlet exciton fission. These properties are discussed in the context of the size of the zethrene core and of its substitution. The work encompasses all known long zethrenes and makes use of a variety of experimental techniques, such as Raman, UV-Vis-NIR absorption, transient absorption, in situ spectroelectrochemistry and quantum chemical calculations. This study reveals how the insertion of suitable molecular modules (i.e., quinoidal) opens the door to new intriguing molecular properties exploitable in organic electronics.

Authors:
; ; ; ;  [1]; ; ;  [2]
  1. Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071 (Spain)
  2. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore)
Publication Date:
OSTI Identifier:
22255164
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 5; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; AROMATIZATION; EXCITED STATES; MOLECULAR STRUCTURE; SPIN ORIENTATION; STABILITY; TRIPLETS

Citation Formats

Zafra, José Luis, González Cano, Rafael C., Ruiz Delgado, M. Carmen, López Navarrete, Juan T., Casado, Juan, Sun, Zhe, Li, Yuan, and Wu, Jishan. Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states. United States: N. p., 2014. Web. doi:10.1063/1.4863557.
Zafra, José Luis, González Cano, Rafael C., Ruiz Delgado, M. Carmen, López Navarrete, Juan T., Casado, Juan, Sun, Zhe, Li, Yuan, & Wu, Jishan. Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states. United States. https://doi.org/10.1063/1.4863557
Zafra, José Luis, González Cano, Rafael C., Ruiz Delgado, M. Carmen, López Navarrete, Juan T., Casado, Juan, Sun, Zhe, Li, Yuan, and Wu, Jishan. 2014. "Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states". United States. https://doi.org/10.1063/1.4863557.
@article{osti_22255164,
title = {Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states},
author = {Zafra, José Luis and González Cano, Rafael C. and Ruiz Delgado, M. Carmen and López Navarrete, Juan T. and Casado, Juan and Sun, Zhe and Li, Yuan and Wu, Jishan},
abstractNote = {A analysis of the electronic and molecular structures of new molecular materials based on zethrene is presented with particular attention to those systems having a central benzo-quinoidal core able to generate Kekulé biradicals whose stability is provided by the aromaticity recovery in this central unit. These Kekulé biradicals display singlet ground electronic states thanks to double spin polarization and have low-energy lying triplet excited states also featured by the aromaticity gain. Pro-aromatization is also the driving force for the stabilization of the ionized species. Moreover, the low energy lying singlet excited states also display a profound biradical fingerprint allowing to singlet exciton fission. These properties are discussed in the context of the size of the zethrene core and of its substitution. The work encompasses all known long zethrenes and makes use of a variety of experimental techniques, such as Raman, UV-Vis-NIR absorption, transient absorption, in situ spectroelectrochemistry and quantum chemical calculations. This study reveals how the insertion of suitable molecular modules (i.e., quinoidal) opens the door to new intriguing molecular properties exploitable in organic electronics.},
doi = {10.1063/1.4863557},
url = {https://www.osti.gov/biblio/22255164}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 5,
volume = 140,
place = {United States},
year = {Fri Feb 07 00:00:00 EST 2014},
month = {Fri Feb 07 00:00:00 EST 2014}
}