Light induced nonlinear optical switch in boronated chromophores: A theoretical search towards high contrast switches in the azobenzene series

Jiménez, Cristina C.; Farfán, Norberto; Romero‐Ávila, Margarita; Santillán, Rosa; Malfant, Isabelle; Lacroix, Pascal G.

doi:10.1016/j.jorganchem.2015.09.035

Cited by 5 publications

(4 citation statements)

References 37 publications

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“…There has been a large number of works devoted to designing azobenzene derivatives with improved properties by using simple theoretical arguments. The leading ideas have been to push the ππ* excitation to lower energies through the incorporation of electron‐withdrawing or ‐donating groups at the ortho and para positions or by extending the π system of the molecule . This has mostly led to systems with the desired redshift in the ππ* excitation but also to a (usually undesired) increase in cis ‐to‐ trans thermal isomerization .…”

Section: Introductionmentioning

confidence: 99%

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF₂‐Coordinated Azo Derivatives

2016

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Recently synthesized BF2 -coordinated azo derivatives have been proposed as photoswitches that operate in the optical window (λ=600-1200 nm) for use in bioimaging applications. Herein, we have theoretically analyzed these compounds and modified some substituents to analyze which properties of the molecule govern its photochemistry. Our results compare rather well with the available experimental data, so our methodology, based on density functional theory (DFT) calculations for the ground electronic state and time-dependent-DFT for the first excited electronic state, is validated. Through systematic modification of different substituents of the parent system, we designed compounds that are predicted to operate fully within the optical window. We also analyzed several molecules for which the cis isomer is the more stable isomer, a quite unusual result for azobenzene derivatives that is a much coveted property for some applications of these photoactive molecules in pharmacology. Our results also provide insight into other properties relevant for photoswitches, such as the thermal stability of the less stable isomer and the magnitude of the gap between the wavelengths of the radiation that activates each isomerization process, which must be as large as possible to improve the yield of each photoisomerization. From a more general perspective, our results may provide a step towards the rational design of new photoswitches that fulfill a set of desired characteristics.

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Section: Introductionmentioning

confidence: 99%

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF₂‐Coordinated Azo Derivatives

2016

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“…The dichroism ratio between the maximum and minimum SHG signals are estimated to be ≈12, exceeding the recently emerging nonlinear materials, such as Azobenzene SAM and β-[(MQ)ZnCl 3 ] (Figure 5c). [34][35][36][37][38][39][40][41] Besides, we can facilely control and tune its SHG effects by regulating the polarization-angles of incident laser. As far as we are aware, this is the first time to achieve tunable SHG properties in 2D multilayered hybrid perovskite ferroelectrics, behaving as an evidence to the strong coupling between the SHG effect and ferroelectricity.…”

Section: Resultsmentioning

confidence: 99%

The First Improper Ferroelectric of 2D Multilayered Hybrid Perovskite Enabling Strong Tunable Polarization‐Directed Second Harmonic Generation Effect

Wang

Guo

et al. 2021

Adv Funct Materials

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2D organometallic halide perovskites are recently emerging as a robust family of ferroelectrics, of which their inherent spontaneous polarization (Ps) endows fascinating quadratic nonlinear optical properties. However, up to date, few studies are reported to tune and control the second harmonic generation (SHG) effect in this ferroelectric branch. Herein, the first improper ferroelectric of 2D multilayered hybrid perovskites, (IA)2(EA)2Pb3Br10 (1, where IA is isoamylammonium and EA is ethylammonium), which exhibits a high Curie temperature (≈371 K) and biaxial ferroelectricity with Ps of 2.2 µC cm−2 is reported. Strikingly, its unique in‐plane ferroelectricity allows strong tunable SHG properties under the polarized‐light. That is, the maximum SHG signals are observed with polarized‐light parallel to Ps, while the minimum SHG appears along the vertical direction. This SHG anisotropy creates an extremely large dichroism ratio of ≈12, as visualized by 2D color mapping, which is the record‐high merit for this type of SHG systems. To the best knowledge, this is the first time to achieve tunable SHG effects through ferroelectric polarization. As a pioneering study, the coupling between the SHG effect and ferroelectricity paves a new direction of 2D hybrid perovskite ferroelectrics toward smart optical device applications.

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“…The differences between the two kinds of chromophores are the rigidization of the azo group and the presence of an electron-deficient BF 2 -core, which formed a more efficient acceptor [ 46 ] in the case of dyes 5–8 . The biggest bathochromic shift was observed for dyes 5 and 6 (with the most electron-donating substituent) [ 42 ]. They absorbed at about 60–100 nm longer wavelengths compared to their parent, non-complexed dyes ( Figure 5 a).…”

Section: Resultsmentioning

confidence: 99%

“…1-Phenylazonaphthalen-2-ole Difluoroborane ( 8 ) Red solid, yield 40%, m.p. 143–145 °C (175–176 °C [ 40 , 41 , 42 ]). 1 H NMR (CDCl 3 from TMS) δ (ppm): 8.63 (d, 1H, 3 J H , H = 7.84 Hz), 8.19 (d, 1H, 3 J H , H = 9.08 Hz), 8.14 (m, 2H), 7.87 (d, 1H, 3 J H , H = 8.00 Hz), 7.77 (m, 1H), 7.59 (m, 4H), 7.31 (s, 1H).…”

Section: Methodsmentioning

confidence: 99%

Substituent and Solvent Polarity on the Spectroscopic Properties in Azo Derivatives of 2-Hydroxynaphthalene and Their Difluoroboranes Complexes

Skotnicka

Czeleń

2021

Materials

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Novel fluorescent dyes such as difluoroborane complexes of 1-phenylazonaphthalen-2-ol derivatives were successfully synthesized and characterized with a focus on the influence of a substituent and a solvent on the basic photophysical properties. 1H, 11B, 13C, 15N, and 19F nuclear magnetic resonance (NMR) spectra of substituted 1-phenylazonaphthalen-2-ol difluoroboranes and their parent azo dyes were recorded and discussed. The absorption and emission properties of synthesized compounds were investigated in solvents of varying polarity. They were found to be fluorescent despite the presence of the azo group. The azo group rotation was blocked by complexing with -BF2 to get a red shift in absorption. Solvent-dependent spectral properties of compounds were investigated using Lipper-Mataga and Bakhshiev plot. The calculated DFT energies and Frontier Molecular Orbitals calculations of the studied compounds were proved to be consistent with the experimental observations.

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Light induced nonlinear optical switch in boronated chromophores: A theoretical search towards high contrast switches in the azobenzene series

Cited by 5 publications

References 37 publications

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF₂‐Coordinated Azo Derivatives

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF₂‐Coordinated Azo Derivatives

The First Improper Ferroelectric of 2D Multilayered Hybrid Perovskite Enabling Strong Tunable Polarization‐Directed Second Harmonic Generation Effect

Substituent and Solvent Polarity on the Spectroscopic Properties in Azo Derivatives of 2-Hydroxynaphthalene and Their Difluoroboranes Complexes

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Light induced nonlinear optical switch in boronated chromophores: A theoretical search towards high contrast switches in the azobenzene series

Cited by 5 publications

References 37 publications

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF2‐Coordinated Azo Derivatives

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF2‐Coordinated Azo Derivatives

The First Improper Ferroelectric of 2D Multilayered Hybrid Perovskite Enabling Strong Tunable Polarization‐Directed Second Harmonic Generation Effect

Substituent and Solvent Polarity on the Spectroscopic Properties in Azo Derivatives of 2-Hydroxynaphthalene and Their Difluoroboranes Complexes

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The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF₂‐Coordinated Azo Derivatives

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF₂‐Coordinated Azo Derivatives