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Quertinmont J, Beaujean P, Stiennon J, et al. Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches. J Phys Chem B. 2021;125(15):3918-3931doi: 10.1021/acs.jpcb.1c01962.
Quertinmont, J., Beaujean, P., Stiennon, J., Aidibi, Y., Leriche, P., Rodriguez, V., Sanguinet, L., & Champagne, B. (2021). Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches. The journal of physical chemistry. B, 125(15), 3918-3931. https://doi.org/10.1021/acs.jpcb.1c01962
Quertinmont, Jean, et al. "Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches." The journal of physical chemistry. B vol. 125,15 (2021): 3918-3931. doi: https://doi.org/10.1021/acs.jpcb.1c01962
Quertinmont J, Beaujean P, Stiennon J, Aidibi Y, Leriche P, Rodriguez V, Sanguinet L, Champagne B. Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches. J Phys Chem B. 2021 Apr 22;125(15):3918-3931. doi: 10.1021/acs.jpcb.1c01962. Epub 2021 Apr 14. PMID: 33851843.
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J Phys Chem B. 2021 Apr 22;125(15):3918-3931. doi: 10.1021/acs.jpcb.1c01962. Epub 2021 Apr 14.

Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches.

The journal of physical chemistry. B

Jean Quertinmont, Pierre Beaujean, Julien Stiennon, Youssef Aidibi, Philippe Leriche, Vincent Rodriguez, Lionel Sanguinet, Benoît Champagne

Affiliations

  1. Theoretical Chemistry Laboratory, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter, University of Namur, B-5000 Namur, Belgium.
  2. Univ Angers, CNRS, MOLTECH-Anjou, F-49000 Angers, France.
  3. Institut des Sciences Moléculaires (ISM, UMR CNRS 5255), Université de Bordeaux, 351 Cours de la Libération, 33405 Talence, France.

PMID: 33851843 DOI: 10.1021/acs.jpcb.1c01962

Abstract

Molecular switches are chemical compounds exhibiting the possibility of reversible transformations between their different forms accompanied by a modification in their properties. Among these, switching of multi-addressable Benzazolo-OXazolidines (BOXs) from a closed form to an open form results in drastic modifications in their linear and nonlinear optical properties. Here, we target molecules containing two identical BOX units (DiBOX) connected by different π-conjugated linkers, and we combine synthesis, UV/visible absorption, and hyper-Rayleigh scattering (HRS) measurements, together with density functional theory (DFT) calculations. Three derivatives have been considered, which differ by the linker: (i) a bithiophene moiety (Bt), (ii) two 3,4-ethylenedioxythiopene (EDOT) units, and (iii) a triad composed of an EDOT-thiophene-EDOT sequence (TtO). As a matter of fact, these systems can adopt three states (CF-CF, POF-POF, and CF-POF) depending on the closed form (CF) or the protonated open form (POF) of each BOX unit. Despite chemical equivalence, stepwise switching of such systems under the addition of a chemical acid or an oxidant has been experimentally evidenced for two of them (DiBOX-Bt and DiBOX-TtO). Then, DFT calculations show that the first BOX opening leads to the formation of a push-pull π-conjugated segment, exhibiting a huge increase in the first hyperpolarizability (β) and a bathochromic shift with respect to the fully closed form. On the contrary, the second BOX opening induces not only a slight bathochromic shift but also a reduction in their β values conferring the great and uncommon abilities to modulate their linear and nonlinear properties over three discrete levels. Among these results, those on DiBOX-Bt agree with the experimental data obtained by HRS measurements and further shed light on their structure-property relationship.

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