Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation
This contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by <i>π</i>-linkers, along their successive opening/closing. Under the fully closed forms,...
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| Format: | Article |
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MDPI AG
2022-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/9/2770 |
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| author | Pierre Beaujean Lionel Sanguinet Vincent Rodriguez Frédéric Castet Benoît Champagne |
| author_facet | Pierre Beaujean Lionel Sanguinet Vincent Rodriguez Frédéric Castet Benoît Champagne |
| author_sort | Pierre Beaujean |
| collection | DOAJ |
| description | This contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by <i>π</i>-linkers, along their successive opening/closing. Under the fully closed forms, all of them display negligible first hyperpolarizability (<i>β</i>) values. When one BOX is opened, which is sketched as <b>C</b>→<b>O</b>, a push–pull <i>π</i>-conjugated segment is formed, having the potential to enhance <i>β</i> and to set the depolarization ratio (DR) to its one-dimensional-like value (DR = 5). This is observed when only one BOX is open, either for the monoBOX species (<b>C</b>→<b>O</b>) or for the diBOX (<b>CC</b>→<b>CO</b>) and triBOX (<b>CCC</b>→<b>CCO</b>) compounds, i.e., when the remaining BOXs stay closed. The next BOX openings have much different effects. For the diBOXs, the second opening (<b>CO</b>→<b>OO</b>) is associated with a decrease of <i>β</i>, and this decrease is tuned by controlling the conformation of the <i>π</i>-linker, i.e., the centrosymmetry of the whole compound because <i>β</i> vanishes in centrosymmetric compounds. For the triBOXs, the second opening gives rise to a <i>Λ</i>-shape compound, with a negligible change of <i>β</i>, but a decrease of the DR whereas, along the third opening, <i>β</i> remains similar and the DR decreases to the typical value of octupolar systems (DR = 1.5). |
| first_indexed | 2024-03-10T03:54:57Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T03:54:57Z |
| publishDate | 2022-04-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-bb2970022f7848afba9117eab89c1c052023-11-23T08:49:20ZengMDPI AGMolecules1420-30492022-04-01279277010.3390/molecules27092770Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry InvestigationPierre Beaujean0Lionel Sanguinet1Vincent Rodriguez2Frédéric Castet3Benoît Champagne4Theoretical Chemistry Laboratory, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter, University of Namur, B-5000 Namur, BelgiumMOLTECH-Anjou (CNRS-UMR 6200), Université d’Angers, F-49045 Angers, FranceCNRS, Bordeaux INP, ISM, Univ. Bordeaux, UMR 5255, F-33400 Talence, FranceCNRS, Bordeaux INP, ISM, Univ. Bordeaux, UMR 5255, F-33400 Talence, FranceTheoretical Chemistry Laboratory, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter, University of Namur, B-5000 Namur, BelgiumThis contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by <i>π</i>-linkers, along their successive opening/closing. Under the fully closed forms, all of them display negligible first hyperpolarizability (<i>β</i>) values. When one BOX is opened, which is sketched as <b>C</b>→<b>O</b>, a push–pull <i>π</i>-conjugated segment is formed, having the potential to enhance <i>β</i> and to set the depolarization ratio (DR) to its one-dimensional-like value (DR = 5). This is observed when only one BOX is open, either for the monoBOX species (<b>C</b>→<b>O</b>) or for the diBOX (<b>CC</b>→<b>CO</b>) and triBOX (<b>CCC</b>→<b>CCO</b>) compounds, i.e., when the remaining BOXs stay closed. The next BOX openings have much different effects. For the diBOXs, the second opening (<b>CO</b>→<b>OO</b>) is associated with a decrease of <i>β</i>, and this decrease is tuned by controlling the conformation of the <i>π</i>-linker, i.e., the centrosymmetry of the whole compound because <i>β</i> vanishes in centrosymmetric compounds. For the triBOXs, the second opening gives rise to a <i>Λ</i>-shape compound, with a negligible change of <i>β</i>, but a decrease of the DR whereas, along the third opening, <i>β</i> remains similar and the DR decreases to the typical value of octupolar systems (DR = 1.5).https://www.mdpi.com/1420-3049/27/9/2770nonlinear opticsmolecular switchsecond-order NLO responseNLO switchbenzazolooxazolidine |
| spellingShingle | Pierre Beaujean Lionel Sanguinet Vincent Rodriguez Frédéric Castet Benoît Champagne Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation Molecules nonlinear optics molecular switch second-order NLO response NLO switch benzazolooxazolidine |
| title | Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation |
| title_full | Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation |
| title_fullStr | Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation |
| title_full_unstemmed | Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation |
| title_short | Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation |
| title_sort | multi state second order nonlinear optical switches incorporating one to three benzazolo oxazolidine units a quantum chemistry investigation |
| topic | nonlinear optics molecular switch second-order NLO response NLO switch benzazolooxazolidine |
| url | https://www.mdpi.com/1420-3049/27/9/2770 |
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