Photoinduced Pedalo‐Type Motion in an Azodicarboxamide‐Based Molecular Switch

Amirjalayer, Saeed; Martínez-Cuezva, Alberto; Berná, José; Woutersen, Sander; Buma, Wybren Jan

doi:10.1002/ange.201709666

Cited by 8 publications

(5 citation statements)

References 69 publications

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“…To support atomistic interpretation, we simulated the transient IR spectra both in gas-phase and in chloroform (using the dynamics reported in our previous study [ 15 ]), following the procedure illustrated in the Methods section. In the following, we compare the simulated spectrum in chloroform with the experiment (the gas-phase spectrum is reported in Figures S4 and S5 in the SI ) [ 14 ]. In particular, we focus on the carbonyl stretching absorbing in the spectral window 1600–1800 cm −1 .…”

Section: Resultsmentioning

confidence: 99%

“…The recently reported peculiar behavior of azodicarboxamide to undergo a volume-conserving pedalo -type decay mechanism upon excitation has attracted attention due to the potential exploration as a molecular switch in confined environments [ 14 , 15 ]. In contrast to chemically related dyes containing a central diazo unit, such as azobenzene, azodicarboxamide does not undergo volume-demanding cis-trans isomerization.…”

Section: Discussionmentioning

confidence: 99%

“…The experimental spectrum was recorded in the frequency range associated with the carbonyl stretching [ 14 ]. For both types of light-induced mechanisms— pedalo -type motion and trans-cis isomerization—the C=O groups are not directly involved but rather act as a spectator mode of the nuclear dynamics, whose frequencies are modulated in the course of the internal conversion in response to the changing electronic structure.…”

Section: Methodsmentioning

confidence: 99%

“…Recently, a novel molecular photo-switch based on the azodicarboxamide chromophore unit ( Figure 1 ) stepped into the spotlight thanks to a unique feature: an ultrafast photoinduced volume-conserving motion. Time-resolved UV-pump/IR-probe spectroscopy [ 14 ] supplemented with QM(TDDFT)/MM non-adiabatic molecular dynamics simulation on the solvated model [ 15 ] demonstrated that the chromophore, in contrast to other azo-compounds, does not undergo the usual trans-cis photoisomerization but rather a volume-conserving pedalo -type motion, rendering possible the application of this new class of chromophores under constrained conditions such as in solid state [ 16 ], on surfaces [ 17 , 18 ] and inside polymers [ 19 ].…”

Section: Introductionmentioning

confidence: 99%

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Modus Operandi of a Pedalo-Type Molecular Switch: Insight from Dynamics and Theoretical Spectroscopy

et al. 2023

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Molecular switches which can be triggered by light to interconvert between two or more well-defined conformation differing in their chemical or physical properties are fundamental for the development of materials with on-demand functionalities. Recently, a novel molecular switch based on a the azodicarboxamide core has been reported. It exhibits a volume-conserving conformational change upon excitation, making it a promising candidate for embedding in confined environments. In order to rationally implement and efficiently utilize the azodicarboxamide molecular switch, detailed insight into the coordinates governing the excited-state dynamics is needed. Here, we report a detailed comparative picture of the molecular motion at the atomic level in the presence and absence of explicit solvent. Our hybrid quantum mechanics/molecular mechanics (QM/MM) excited state simulations reveal that, although the energy landscape is slightly modulated by the solvation, the light-induced motion is dominated by a bending-assisted pedalo-type motion independent of the solvation. To support the predicted mechanism, we simulate time-resolved IR spectroscopy from first principles, thereby resolving fingerprints of the light-induced switching process. Our calculated time-resolved data are in good agreement with previously reported measured spectra.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Modus Operandi of a Pedalo-Type Molecular Switch: Insight from Dynamics and Theoretical Spectroscopy

et al. 2023

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“…The electronically exited state involved in the switching process was also poorly dealt with by a standard DFT. In this case, the time-dependent density functional theory provide novel solution to accurately describe the energies, structures, and properties of excited states during the switching process, [167][168][169] which now is still in lacking.…”

Section: Summary and Perspectivementioning

confidence: 99%

One molecule, two states: Single molecular switch on metallic electrodes

Liu

Yang

et al. 2020

WIREs Comput Mol Sci

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The state‐of‐the‐art density functional theory (DFT) has become an essential tool for the investigation and development of molecular electronics at the electronic and atomic level. In this review paper, we show several typical examples to demonstrate that the DFT approaches, combined with nonequilibrium Green's function method, are able to design many prominent molecular switches—the most fundamental component in molecular electronics that can be utilized in information storage and logic gates. We mainly review the progress and important features of four remarkable switches with distinct transition mechanisms: (a) azobenzene‐like switches based on the cis–trans isomerization; (b) diarylethene‐like switches based on open‐closed transition; (c) porphyrin‐like switches based on tautomerizations; and (d) benzene‐like switches based on the physisorbed state and chemisorbed state. Special attentions have been paid on the molecular configuration, switching mechanism, and the role of van der Waals forces between the molecules and the metallic electrodes. We also summarize the avenues to effectively tailor the bistability, reversibility, and transport properties of these systems. This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Density Functional Theory

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Light‐Driven Reversible Intermolecular Proton Transfer at Single‐Molecule Junctions

et al. 2019

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Photoresponsive molecular systems are essential for molecular optoelectronic devices, but most molecular building blocks are non‐photoresponsive. Employed here is a photoinduced proton transfer (PIPT) strategy to control charge transport through single‐molecule azulene junctions with visible light under ambient conditions, which leads to a reversible and controllable photoresponsive molecular device based on non‐photoresponsive molecules and a photoacid. Also demonstrated is the application of PIPT in two single‐molecule AND gate and OR gate devices with electrical signal as outputs.

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Photoinduced Pedalo‐Type Motion in an Azodicarboxamide‐Based Molecular Switch

Cited by 8 publications

References 69 publications

Modus Operandi of a Pedalo-Type Molecular Switch: Insight from Dynamics and Theoretical Spectroscopy

Modus Operandi of a Pedalo-Type Molecular Switch: Insight from Dynamics and Theoretical Spectroscopy

One molecule, two states: Single molecular switch on metallic electrodes

Light‐Driven Reversible Intermolecular Proton Transfer at Single‐Molecule Junctions

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