Hemiindigoids As Prominent Photoswitch Scaffolds DOI Creative Commons
Aurélie Gernet,

Loïc Toursel,

Louise‐Marie Balivet

et al.

ChemPhotoChem, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 22, 2024

Abstract Hemiindigo photoswitches, a class of chromophores derived from the well‐known indigo dye, have attracted considerable interest over past two decades. These compounds are unique in their ability to absorb light visible region spectrum both isomeric states, making them ideal for applications where high‐energy UV is not tolerated. A particularly attractive feature hemiindigoids that, despite rigid structures, they undergo significant and controllable changes during photoisomerisation process. Moreover, exhibit combination high thermal bistability, pronounced photochromism, fast, efficient photoisomerisation, positioning hemiindigoid photoswitches as versatile chromophores. This review summarises current developments advances including synthesis, photoswitching performance, applications, with strong focus on practical use reversible triggers fields ranging photopharmacology advanced materials.

Language: Английский

Excited State Dynamics in Unidirectional Photochemical Molecular Motors DOI Creative Commons
Palas Roy, Andy S. Sardjan, Wesley R. Browne

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12255 - 12270

Published: April 24, 2024

Unidirectional photochemically driven molecular motors (PMMs) convert the energy of absorbed light into continuous rotational motion. As such they are key components in design machines. The prototypical and most widely employed class PMMs is overcrowded alkenes, where motion by successive photoisomerization thermal helix inversion steps. efficiency depends upon speed rotation, determined rate ground state inversion, quantum yield photoisomerization, which dependent on excited landscape. former has been optimized synthetic modification across three generations alkene PMMs. These improvements have often at expense yield, there remains room for improvement. In this perspective we review application ultrafast spectroscopy to characterize dynamics measurements lead a general mechanism all PMMs, involving subpicosecond decay Franck–Condon populate dark decays within picoseconds via conical intersections with electronic state. model discussed context calculations. Studies PMM photochemical as function solvent suggest exploitation intramolecular charge transfer polarity route controlling yield. A test these ideas first generation motor reveals high degree control over isomerization results pathway fine performance future

Language: Английский

Citations

7
Photoswitchable Molecular Motor Phospholipid: Synthesis, Characterization, and Integration into Lipid Vesicles DOI Creative Commons
Ainoa Guinart, Daniel Doellerer, Yusuf Qutbuddin

et al.

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

Published: Feb. 3, 2025

Lipid membranes are essential for cellular function, acting as barriers and platforms major biochemical activities. The integration of photoisomerizable units into lipid structures allows tunable membrane properties, offering insights membrane-related processes. In this study, we present the first molecular-motor-conjugated phospholipid system. synthesis two phosphatidylcholine derivatives is reported, where one acyl chain replaced with a light-responsive molecular rotary motor moiety. We explore photochemical thermodynamic behaviors these compounds in solution self-assembled systems, demonstrating their rotation cycles under illumination dynamic properties combination molecules. Additionally, giant unilamellar vesicles formed to investigate mechanisms photoinduced responses synthetic membranes. Our findings show that motor-based lipids can operate aqueous natural phospholipids, maintaining photoisomerization enabling oxidation-driven release within vesicles.

Language: Английский

Citations

0
Hemiphosphoindigos as a platform for chiroptical or water soluble photoswitching DOI Creative Commons

Fabien Kohl,

Thomas Vogl, Frank Hampel

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 19, 2025

Abstract Photoswitches are important molecular tools to precisely control the behavior of matter by using light irradiation. They have found application in virtually all applied chemical fields from biology material sciences. However, great challenges remain advanced property design including tailored chiroptical responses or water solubility. Here, hemiphosphoindigo (HPI) photoswitches presented as capable phosphorus-based and a distinct addition established indigoid chromophore family. Phosphinate is embedded core resulting optimized display high thermal stabilities, excellent fatigue resistance isomer enrichment. A series planar, twisted heterocyclic HPIs investigated probe strategies for advantageous photophysical properties. The phosphinate provides platform easily accessible, water-soluble photoswitches, especially interesting biological applications. Its chiral nature further allows light-induced modulation therefore open up structural space photoswitch generation light-responsive

Language: Английский

Citations

0
Directionality Reversal and Shift of Rotational Axis in a Hemithioindigo Macrocyclic Molecular Motor DOI Creative Commons

Lilli Reißenweber,

Edgar Uhl,

Frank Hampel

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23387 - 23397

Published: Aug. 7, 2024

Molecular motors are central driving units for nanomachinery, and control of their directional motions is fundamental importance functions. Light-driven variants use easy to provide, dose, waste-free fuel with high energy content, making them particularly interesting applications. Typically, light-driven molecular work via rotations around dedicated chemical bonds where the directionality rotation dictated by steric effects asymmetry in close vicinity axis. In this work, we show how unidirectional a virtual axis can be realized reprogramming motor. To end, classical motor restricted macrocyclization, its intrinsic transformed into macrocyclic chain opposite direction. Further, solvent polarity changes allow toggle function machine between nondirectional photoswitch. way, new concept design delivered together elaborate over functions simple changes. The possibility sensing environmental correspondingly adjusting opens up next level responsiveness nanoscopic motors.

Language: Английский

Citations

3
A Proof‐of‐Principle Design for Through‐Space Transmission of Unidirectional Rotary Motion by Molecular Photogears** DOI Creative Commons
Enrique M. Arpa, S. Stafström, Bo Durbeej

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(2)

Published: Oct. 31, 2023

The construction of molecular photogears that can achieve through-space transmission the unidirectional double-bond rotary motion light-driven motors onto a remote single-bond axis is formidable challenge in field artificial machines. Here, we present proof-of-principle design such based on possibility using stereogenic substituents to control both relative stabilities two helical forms photogear and photoisomerization reaction connects them. potential was verified by quantum-chemical modeling through which photogearing found be favorable process compared free-standing rotation ("slippage"). Overall, our study unveils surprisingly simple approach realizing photogearing.

Language: Английский

Citations

5
The rapid synthesis of 1,10-phenanthroline-5,6-diimine (Phendiimine) and its fascinating photo-stimulated behavior DOI Creative Commons
Ghasem Marandi, Ali Hassanzadeh

Scientific Reports, Journal Year: 2024, Volume and Issue: 14(1)

Published: April 11, 2024

Abstract Here, for the first time, we report synthesis of 1,10-phenanthroline-5,6-diimine (Phendiimine) based on an acid catalysed SN 2 reaction 1,10-phenanthroline-5,6-dione and 2-picolylamine in EtOH as a solvent. The synthesized Phendiimine molecule showed excellent photo-sensitivity against visible light, together with photoluminescence both water ethanol also, it electrochemical activity Fe electrode H SO 4 solution. Tauc plot also is direct band-gap semiconductor. hot-point probe test that n-type UV–vis. absorption maximum shift two solvents (water ethanol) demonstrates solvatochromism behavior molecule. practical significance this work its guiding implication future related research can be outlined follows. Based results obtained, appears could revolutionize medical field, potentially design artificial eyes, increasing yield photovoltaic cells through enhanced heat transfer, improving computers industrial photo-cooling systems, serving photo-controller place piezoelectric devices, functioning electronic opt couplers, controlling remote lasers, changing convection photothermal heaters, designing miniaturized real photo-stimulated motors, creating photo or thermal switches spin crossover complexes, developing light-dependent resistance (LDR) constructing X-ray gamma-ray detectors, intelligent clothing, dynamic tumour therapy (PDT) singlet fission materials solar more.

Language: Английский

Citations

1
Directionality Reversal and Shift of Rotational Axis in a Hemithioindigo Macrocyclic Molecular Motor DOI Creative Commons

Lilli Reißenweber,

Edgar Uhl,

Frank Hampel

et al.

Published: April 23, 2024

Molecular motors are central driving units for nanomachinery and control of their directional motions is fundamental importance functions. Light-driven variants use an easy to provide, dose, waste free fuel with high energy content, which makes them particularly interesting many applications. Typically, light-driven molecular work via rotations around dedicated chemical bonds (e.g. double bonds) where directionality the rotation dictated by steric effects asymmetry in close vicinity axis. In this we show how unidirectional a virtual axis can be realized reprogramming motor. To end, classical motor restricted macrocyclization its intrinsic transformed into macrocyclic chain opposite direction. Further, solvent polarity changes allow toggle function machine between non-directional photoswitch. way new concept design delivered together elaborate over functions simple changes. The possibility sensing environmental correspondingly adjusting opens up next level responsiveness nanoscopic motors.

Language: Английский

Citations

1
Quantifying macrocyclization-induced strain utilizing N-phenylimides as conformational reporters DOI
Bright U. Emenike,

David W. Shinn,

Ronald A. Spinelle

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(30), P. 4040 - 4043

Published: Jan. 1, 2024

Incorporating an N -phenylimide unit into macrocycles enabled measurements of macrocyclization strains by comparing the -phenylimide's conformational changes to similar units attached a linear-chain control.

Language: Английский

Citations

0
Coupling Rotary Motion to Helicene Inversion within a Molecular Motor DOI Creative Commons
Yohan Gisbert, Marco Ovalle, Charlotte N. Stindt

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Towards complex coupled molecular motions, the remote handedness inversion of a helicene moiety was achieved by rotary motor. The use specifically engineered dynamic stator in novel overcrowded-alkene second-generation motor based on fluorinated dibenzofluorene fragment allows for an unprecedented control over helicity inversion. This is mechanical coupling rotation rotor to half via chirality transmission process. Thus, unidirectional motion generated upon irradiation used invert stereochemistry helicene, leading 6-step cycle with eight intermediates. In this cycle, both alternation between P and M configurations thermal interconversion (paddling motion) can be achieved. In-depth computational spectroscopic studies were performed support associated mechanism. offers prospects development responsive systems.

Language: Английский

Citations

0
Coupling Rotary Motion to Helicene Inversion within a Molecular Motor DOI Creative Commons
Yohan Gisbert, Marco Ovalle, Charlotte N. Stindt

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Abstract Towards complex coupled molecular motions, the remote handedness inversion of a helicene moiety was achieved by rotary motor. The use specifically engineered dynamic stator in novel overcrowded‐alkene second‐generation motor based on fluorinated dibenzofluorene fragment allows for an unprecedented control over helicity inversion. This is mechanical coupling rotation rotor to half via chirality transmission process. Thus, unidirectional motion generated upon irradiation used invert stereochemistry helicene, leading 6‐step cycle with eight intermediates. In this cycle, both alternation between P and M configurations thermal interconversion (paddling motion) can be achieved. In‐depth computational spectroscopic studies were performed support associated mechanism. offers prospects development responsive systems.

Language: Английский

Citations

0