Quantum‐Classical Simulations Reveal the Photoisomerization Mechanism of a Prototypical First‐Generation Molecular Motor DOI Creative Commons
Davide Accomasso, Joanna Jankowska

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 30, 2024

Abstract Light‐driven molecular rotary motors convert the energy of absorbed light into unidirectional rotational motion and are key components in design machines. The archetypal class light‐driven is chiral overcrowded alkenes, where movement achieved through consecutive cis‐trans photoisomerization reactions thermal helix inversion steps. While steps have been rather well understood by now, our understanding alkene‐based still misses points that would explain striking differences operation efficiency known systems. Here, we employ quantum‐chemical calculations nonadiabatic dynamics simulations to investigate excited‐state decay mechanism a prototypical first‐generation motor. We show initially excited bright state undergoes an ultrafast relaxation multiple minima separated low barriers reveal slow picosecond‐timescale ground state, which only occurs from largely twisted dark minimum, far any conical‐intersection point. Additionally, attribute origin high yields forward investigated motor favorable topography ground‐state potential surface, controlled conformation central cyclopentene rings.

Language: Английский

A Cost‐Effective Computational Strategy for the Electronic Layout Characterization of a Second Generation Light‐Driven Molecular Rotary Motor in Solution DOI Creative Commons
Raoul Carfora, Federico Coppola,

Paola Cimino

et al.

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(2)

Published: Jan. 11, 2025

ABSTRACT Light‐driven molecular rotary motors are nanometric machines able to convert light into unidirectional motions. Several types of have been developed better respond stimuli, opening new avenues for developing smart materials ranging from nanomedicine robotics. They great importance in the scientific research across various disciplines, but a detailed comprehension underlying ultrafast photophysics immediately after photo‐excitation, that is, Franck–Condon region characterization, is not fully achieved yet. For this aim, it first required rely on an accurate description at ab initio level system potential energy before performing any further step, dynamics. Thus, we present extensive investigation aimed accurately describing electronic structure low‐lying states (electronic layout) rotor region, belonging class overcrowded alkenes: 9‐(2‐methyl‐2,3‐dihydro‐1H‐cyclopenta[a]naphthalen‐1‐ylidene)‐9H‐fluorene. This was chosen since its very interesting more general understanding similar compounds used as rotors, where can be found (whose energetic interplay crucial dynamics) and presence different substituents tune HOMO‐LUMO gap. scope, employed theory levels within time‐dependent density functional framework, presenting also careful comparison adopting post Hartree–Fock methods characterizing conformations involved photocycle. Effects layout functionals, basis sets, environment descriptions, role dispersion correction were all analyzed detail. In particular, treatment solvent effects here considered depth, showing how implicit excited by testing both linear‐response state‐specific formalisms. As main results, chose two cost‐effective (accurate relatively cheap) ground state verified choosing these influence curvature via frequency analysis normal modes vibrations active Raman spectrum. theoretical survey step towards feasible characterization early stage solution during photoisomerization processes wherein multiple might populated upon radiation, leading future molecular‐level interpretation time‐resolved spectroscopies.

Language: Английский

Citations

1
General strategy for boosting the performance of speed-tunable rotary molecular motors with visible light DOI Creative Commons
Jinyu Sheng, Carlijn L. F. van Beek, Charlotte N. Stindt

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(8)

Published: Feb. 19, 2025

Light-driven molecular rotary motors perform chirality-controlled unidirectional rotations fueled by light and heat. This unique function renders them appealing for the construction of dynamic systems, actuating materials, machines. Achieving a combination high photoefficiency, visible-light responsiveness, synthetic accessibility, easy tuning properties within single scaffold is critical these applications but remains longstanding challenge. Herein, series highly photoefficient visible-light–responsive (MMs), featuring various speeds, was obtained convenient one-step formylation their parent motors. strategy greatly improves all aspects performance MMs—red-shifted wavelengths excitation, photoisomerization quantum yields, photostationary state distributions isomers—beyond state-of-the-art light-responsive MM systems. The development this late-stage functionalization MMs opens avenues high-performance machines devices in materials science biological representing major advance toolbox

Language: Английский

Citations

1
From nano to macro: Light‐driven chiral dopants in liquid crystals DOI Creative Commons
Yang Zhang, Ruoling Liu, Jiawen Chen

et al.

Deleted Journal, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Abstract Harnessing nanoscale molecular structural changes to achieve precise control over macroscopic devices represents an emerging and effective strategy. One promising approach involves the introduction of light‐driven chiral dopants into liquid crystals (LCs), enabling fine‐tuned modulation helical superstructures in cholesteric (CLCs) via photoisomerization. This strategy opens up exciting possibilities for development innovative photo‐responsive with dynamic functionalities. review focuses on most common used LCs, including azobenzene, diarylethene, α ‐cyanostilbene overcrowded alkene. The chemical design principles these four types switches are highlighted, along their abilities induce pitch inversion CLCs. Finally, applications controlling showcased, particularly display technologies, anti‐counterfeiting, optical 3D droplet manipulation. It is hoped that this provides valuable insights guidances novel advancement soft matter material applications.

Language: Английский

Citations

1
Photosensitizers Interactions: From Basic Concepts to Clinical Applications DOI
Anselmo Fortunato Ruiz Rodriguez,

Anderson L. Ramos,

Christiane Pavani

et al.

Published: Jan. 1, 2025

Language: Английский

Citations

0
Non-adiabatic Couplings in Surface Hopping with Tight Binding Density Functional Theory: The Case of Molecular Motors DOI
Gonzalo Díaz Mirón, Carlos R. Lien-Medrano, Debarshi Banerjee

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 20, 2024

Nonadiabatic molecular dynamics (NAMD) has become an essential computational technique for studying the photophysical relaxation of systems after light absorption. These phenomena require approximations that go beyond Born-Oppenheimer approximation, and accuracy results heavily depends on electronic structure theory employed. Sophisticated methods, however, make these techniques computationally expensive, even medium size systems. Consequently, simulations are often performed simplified models to interpret experimental results. In this context, a variety have been developed perform NAMD using approximate particularly density functional tight binding (DFTB). Despite use large systems, where ab initio methods prohibitive, comprehensive validation lacking. work, we present new implementation trajectory surface hopping combined with DFTB, utilizing nonadiabatic coupling vectors. We selected methaniminium cation furan validation, providing exhaustive comparison higher-level methods. As case study, simulated system from class motors, which extensively studied experimentally but remains challenging simulate due its inherent complexity. Our approach effectively captures key mechanism dihedral rotation absorption light. Additionally, successfully reproduced transition bright dark states observed in time-dependent fluorescence experiments, valuable insights into critical part behavior motors.

Language: Английский

Citations

2
On the supramolecular interactions into a pH‐ and Metal‐Actuated Molecular Shuttle: some insights from QTAIM modeling DOI Creative Commons
Costantino Zazza, Nico Sanna, Stefano Borocci

et al.

ChemPhysChem, Journal Year: 2024, Volume and Issue: 25(23)

Published: Aug. 15, 2024

Abstract Supramolecular contacts responsible for chemical interaction of cucurbit[7]uril ( CB[7] ) macrocycle on a Tolyl‐Viologen‐Phenylene‐Imidazole T‐VPI molecular thread, at acid pH T‐VPI‐H + or after Ag cation addition T‐VPI‐Ag ), are analytically addressed in computational framework combining Quantum Theory Atoms Molecules (QTAIM) with Density Functional (DFT). In this respect, the crystallographic structure (CCDC number 2217466) is taken as reference condition addressing nature interactions driving shuttling between T and P stations recently observed dilute water solutions. Beside host( vs guest( complexation, coordination sphere also investigated by means local electronic energy density ‐ H r descriptors. The derived non‐covalent patterns found to support diagnostic 1 NMR signals used detecting mutual position along axle. This work highlights potentialities QTAIM based approach characterization supramolecular metal‐complexation effects aggregates such not‐interlocked synthetic shuttles.

Language: Английский

Citations

1
Quantum‐Classical Simulations Reveal the Photoisomerization Mechanism of a Prototypical First‐Generation Molecular Motor DOI Creative Commons
Davide Accomasso, Joanna Jankowska

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 30, 2024

Abstract Light‐driven molecular rotary motors convert the energy of absorbed light into unidirectional rotational motion and are key components in design machines. The archetypal class light‐driven is chiral overcrowded alkenes, where movement achieved through consecutive cis‐trans photoisomerization reactions thermal helix inversion steps. While steps have been rather well understood by now, our understanding alkene‐based still misses points that would explain striking differences operation efficiency known systems. Here, we employ quantum‐chemical calculations nonadiabatic dynamics simulations to investigate excited‐state decay mechanism a prototypical first‐generation motor. We show initially excited bright state undergoes an ultrafast relaxation multiple minima separated low barriers reveal slow picosecond‐timescale ground state, which only occurs from largely twisted dark minimum, far any conical‐intersection point. Additionally, attribute origin high yields forward investigated motor favorable topography ground‐state potential surface, controlled conformation central cyclopentene rings.

Language: Английский

Citations

0