Modeling, Preparation, and Characterization of a Dipole Moment Switch Driven by <i>Z</i>/<i>E</i> Photoisomerization

Melloni, Alfonso; Paccani, Riccardo Rossi; Donati, Donato; Zanirato, Vinicio; Sinicropi, Adalgisa; Parisi, Maria Laura; Martin, Elena; Ryazantsev, Mikhail N.; Ding, Wan Jian; Frutos, Luis Manuel; Basosi, Riccardo; Fusi, Stefania; Latterini, Loredana; Ferré, Nicolas; Olivucci, Massimo

doi:10.1021/ja906733q

Cited by 56 publications

(74 citation statements)

References 33 publications

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“…The ring inversions contribute to the torsion around C4C1′ while minimizing the required space and conserving the position of the center of mass of both rings during the early stage of the isomerization dynamics. In the case of ZW‐NAIP, we showed5b that they take place in both the excited‐state trajectory and the minimum energy path, indicating that they are driven by the S 1 force field and, therefore, are part of the reaction coordinate.…”

Section: Computational Resultsmentioning

confidence: 89%

“…For this reason, we focus on two trajectories released from the FC region with no initial kinetic energy and representing limiting cases (see below). These trajectories have been shown to successfully follow the bottom of the excited‐state potential energy valley for ZW‐NAIP 5b. For Rh it has also been shown that changing the initial condition do not qualitatively alter the character of the following molecular motion 12…”

Section: Methodsmentioning

confidence: 94%

“…The resulting scaled‐CASSCF potential provides a MS‐CASPT2‐like excited‐state force field and, therefore, time scales. In this work, we use the scaling factor α =0.535 employed by Melloni et al 5b. for ZW‐NAIP.…”

Section: Methodsmentioning

confidence: 99%

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Mechanistic Origin of the Vibrational Coherence Accompanying the Photoreaction of Biomimetic Molecular Switches

Léonard¹,

Schapiro²,

Briand³

et al. 2012

Chemistry A European J

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101

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The coherent photoisomerization of a chromophore in condensed phase is a rare process in which light energy is funneled into specific molecular vibrations during electronic relaxation from the excited to the ground state. In this work, we employed ultrafast spectroscopy and computational methods to investigate the molecular origin of the coherent motion accompanying the photoisomerization of indanylidene-pyrroline (IP) molecular switches. UV/Vis femtosecond transient absorption gave evidence for an excited- and ground-state vibrational wave packet, which appears as a general feature of the IP compounds investigated. In close resemblance to the coherent photoisomerization of rhodopsin, the sudden onset of a far-red-detuned and rapidly blue-shifting photoproduct signature indicated that the population arriving on the electronic ground state after nonadiabatic decay through the conical intersection (CI) is still very focused in the form of a vibrational wave packet. Semiclassical trajectories were employed to investigate the reaction mechanism. Their analysis showed that coupled double-bond twisting and ring inversions, already populated during the excited-state reactive motion, induced periodic changes in π-conjugation that modulate the ground-state absorption after the non-adiabatic decay. This prediction further supports that the observed ground-state oscillation results from the reactive motion, which is in line with a biomimetic, coherent photoisomerization scenario. The IP compounds thus appear as a model system to investigate the mechanism of mode-selective photomechanical energy transduction. The presented mechanism opens new perspectives for energy transduction at the molecular level, with applications to the design of efficient molecular devices.

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Section: Computational Resultsmentioning

confidence: 89%

Section: Methodsmentioning

confidence: 94%

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Mechanistic Origin of the Vibrational Coherence Accompanying the Photoreaction of Biomimetic Molecular Switches

Léonard¹,

Schapiro²,

Briand³

et al. 2012

Chemistry A European J

Self Cite

101

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show abstract

“…First of all, a family of benzylidene-pyrroline derivatives was synthesized and analyzed by means of CASSCF// CASPT2 theoretical calculations. [11] However, the synthetic route used was complex and hardly adaptable for switches with different substitution groups. 10 -3 ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photoisomerization of Rhodopsin‐Based Molecular Switches

2012

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A new family of switches based on a rhodopsin chromophore is presented. These new photoswitches fulfil most of the required features for an efficient switch to be used in practical applications. The synthetic route is simple and versatile and enables substituents capable of acting as anchoring points to be incorporated. Also, substitution can be used to fine tune the switches' properties. The photostationary state can be reached easily by using low‐energy light compatible with complex environments. Thermal reset allows these switches to operate through on/off cycles.

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“…[16][17][18][19][20] In a series of recent works, [21][22][23] we have applied quantum chemical methods in combination with molecular dynamics simulations to achieve a deeper understanding of the mechanism of photochemical rearrangement in synthetic lightdriven rotary molecular motors, which are based on overcrowded aromatic enylidenes. It is the purpose of the present work to apply advanced quantum chemical calculations of the same type as in refs.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Photochemistry of a Reversible Three‐State Bis‐Thiaxanthylidene Molecular Switch

Filatov

2011

ChemPhysChem

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The ground- and the lowest singlet excited-state potential energy surfaces of the bis-thiaxanthylidene (3) molecular switch are investigated using a density functional method specifically designed to treat molecular systems typified by strong non-dynamic electron correlation. The results of the theoretical calculations suggest that the unique ability of substituted bis-thiaxanthylidenes to switch between three states of luminescence-non-fluorescent state, blue fluorescent state, and red fluorescent state-can be explained by specific features on the excited state potential energy surface: the potential barrier around the Franck-Condon point of the anti-folded conformer and the existence of conical intersection in the vicinity of the syn-folded conformer. It is suggested that the twisted conformer, if made more stable via chemical modification, should fluoresce in the near-infrared region (λ≈740-760 nm), thus offering a possibility for a four-state switching of luminescence in a single-component molecular system.

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Modeling, Preparation, and Characterization of a Dipole Moment Switch Driven by Z/E Photoisomerization

Cited by 56 publications

References 33 publications

Mechanistic Origin of the Vibrational Coherence Accompanying the Photoreaction of Biomimetic Molecular Switches

Mechanistic Origin of the Vibrational Coherence Accompanying the Photoreaction of Biomimetic Molecular Switches

Synthesis and Photoisomerization of Rhodopsin‐Based Molecular Switches

Theoretical Study of the Photochemistry of a Reversible Three‐State Bis‐Thiaxanthylidene Molecular Switch

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