Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches
| Autor: | Pierre Beaujean, Benoît Champagne, Lionel Sanguinet, Jean Quertinmont, Philippe Leriche, Youssef Aidibi, Julien Stiennon, Vincent Rodriguez |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Molecular switch
Oxazolidine Materials science 010304 chemical physics Hyperpolarizability Triad (anatomy) Protonation 010402 general chemistry 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films chemistry.chemical_compound Crystallography medicine.anatomical_structure chemistry 0103 physical sciences Bathochromic shift Materials Chemistry medicine Molecule Density functional theory Physical and Theoretical Chemistry |
| Zdroj: | 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 ', Journal of physical chemistry B, vol. 125, no. 15, pp. 3918-3931 . https://doi.org/10.1021/acs.jpcb.1c01962 |
| DOI: | 10.1021/acs.jpcb.1c01962 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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