Extraordinary Redox Activities in Ladder-Type Conjugated Molecules Enabled by B ← N Coordination-Promoted Delocalization and Hyperconjugation

Zhu, Congzhi; Ji, Xiaozhou; You, Di; Chen, Teresa L.; Mu, Anthony U.; Barker, Kayla P.; Klivansky, Liana M.; Liu, Yi; Fang, Lei

doi:10.1021/jacs.8b11337

Title: Extraordinary Redox Activities in Ladder-Type Conjugated Molecules Enabled by B ← N Coordination-Promoted Delocalization and Hyperconjugation

Journal Article · 02 December 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.8b11337 · OSTI ID:1563988

^[1]; Ji, Xiaozhou ^[1]; You, Di ^[1]; Chen, Teresa L. ^[2]; Mu, Anthony U. ^[1]; Barker, Kayla P. ^[1]; Klivansky, Liana M. ^[2];

^[2];

^[1]

Texas A & M Univ., College Station, TX (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The introduction of B ← N coordinate bond-isoelectronic to C-C single bond-into π-systems represents a promising strategy to impart exotic redox and electrochromic properties into conjugated organic molecules and macromolecules. To achieve both reductive and oxidative activities using this strategy, a cruciform ladder-type molecular constitution was designed to accommodate oxidation-active, reduction-active, and B ← N coordination units into a compact structure. Two such compounds (BN-F and BN-Ph) were synthesized via highly efficient N-directed borylation. These molecules demonstrated well-separated, two reductive and two oxidative electron-transfer processes, corresponding to five distinct yet stable oxidation states, including a rarely observed boron-containing radical cation. Spectroelectrochemical measurements revealed unique optical characteristics for each of these reduced/oxidized species, demonstrating multicolor electrochromism with excellent recyclability. Distinct color changes were observed between each redox state with clear isosbestic points on the absorption spectra. Here, the underlying redox mechanism was elucidated by a combination of computational and experimental investigations. Single-crystal X-ray diffraction analysis on the neutral state, the oxidized radical cation, and the reduced dianion of BN-Ph revealed structural transformations into two distinct quinonoid constitutions during the oxidation and reduction processes, respectively. B ← N coordination played an important role in rendering the robust and reversible multistage redox properties, by extending the charge and spin delocalization, by modulating the π-electron density, and by a newly established hyperconjugation mechanism.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1563988

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 51 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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