Solid-State Photoswitching of Hydrazones Based on Excited-State Intramolecular Proton Transfer

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

The development of new photochromic systems is motivated by the possibility controlling properties and functions materials with high spatial temporal resolution in a reversible manner. While there are several classes photoswitches operating solution, design efficiently solid state remains highly challenging, mainly due to limitations related confinement effects. Triaryl-hydrazones represent relatively subclass bistable hydrazone exhibiting efficient Z/E photochromism solution. As "large volume" photoswitches, they have been anticipated display only limited solid-state photoswitching. Here, we show that Z isomers newly prepared triaryl-hydrazones containing perfluorinated hydrazine phenyl ring (PHZs) exhibit impressive an unexpected light-induced red-shift absorption maximum. Based on (time-dependent) density functional theory calculations, photoswitching reaction mechanism involving excited intramolecular proton transfer has proposed, which rationalizes observed formation metastable structure. Advanced experimental techniques including X-ray diffraction, NMR EPR spectroscopy, confocal Raman microscopy corroborated suggested revealed superficial phenomenon. This atypical behavior PHZs can also be realized using visible light form thin films, manifests their potential use optics optoelectronics.

Language: Английский

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General strategy for boosting the performance of speed-tunable rotary molecular motors with visible light

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

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Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Abstract Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution‐like response stimuli‐responsive moieties solid‐state due intermolecular interactions imposed through close packing bulk solids. As result, integration photochromic compounds into synthetically porous matrices, such metal‐organic frameworks (MOFs), has come forefront an emerging strategy for material development. This review highlights how core principles reticular chemistry (on example MOFs) play critical role performance, surpassing limitations previously observed solution solid state. The symbiotic relationship between photoresponsive and focus on synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy charge transfer, switchable gas sorption, synergistic chromophore communication is discussed. not only focuses recent cutting‐edge advancements development, but also novel, vital‐to‐pursue pathways multifaceted functional realms energy, technology, biomedicine.

Language: Английский

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General Synthetic Methodologies for Building Blocks to Construct Molecular Motors

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Here we present a collection of reliable, high yielding, and efficient synthetic methods for the preparation commonly used building blocks to construct molecular rotary motors based on overcrowded alkenes. The easy access robust synthesis procedures facilitate new endeavors employ in recently emerging fields toward dynamic chemical systems responsive materials.

Language: Английский

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Development of Spiropyran Immobilization and Characterization Protocols for Reversible Photopatterning of SiO₂ Surfaces

ACS Omega, Journal Year: 2024, Volume and Issue: 9(27), P. 29401 - 29409

Published: June 24, 2024

Spiropyran is a dynamic organic compound that distinguished by its reversible conversion between two forms: the colorless closed spiropyran (SP) form and purple open merocyanine (MC) form. Typically triggered UV light reversed visible light, spiropyran-functionalized surfaces offer in properties including color, polarity, reactivity, fluorescence, making them applicable to diverse applications chemical sensors, biosensors, drug delivery, heavy metal extraction. While has been successfully incorporated into various material platforms with SiO2 surfaces, application on flat limited due surface area constraints lack of standardized evaluation methods, which largely depend integration approach substrate type used. In this study, we systematically review existing literature categorize methods types first then report our experimental work, developed streamlined three-step immobilization protocol, includes activation, amination (3-aminopropyl) triethoxysilane (APTES), subsequent functionalization carboxylic (SP-COOH). Using as demonstration, have also established robust characterization consisting contact angle measurements, X-ray photoelectron spectroscopy (XPS), ellipsometry, fluorometric analysis. Our results evaluate newly demonstrating effective activation optimal using 2% APTES solution, achieved 5 min at room temperature. Fluorescence imaging provided clear contrast SP MC forms. Furthermore, discuss limitations density functional groups steric hindrance propose future improvements. work not only underscores versatility patterning but provides optimized protocols for may be adapted use other substrates. These advancements lay groundwork on-chip sensing technologies applications.

Language: Английский

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The integration of multiple components for multi-responsive dynamic framework materials

Matter, Journal Year: 2024, Volume and Issue: 7(8), P. 2766 - 2768

Published: Aug. 1, 2024

Language: Английский

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Exploration of Unconventional excitation wavelength and dynamic emission in rare-earth doped multilayer core-shell Structures: Application for optical “Hard” and “Soft” switching

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 678, P. 283 - 290

Published: Sept. 14, 2024

Language: Английский

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Merocyanines: Electronic Structure and Spectroscopy in Solutions, Solid State, and Gas Phase

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(21), P. 12086 - 12144

Published: Oct. 18, 2024

Merocyanines, owing to their readily tunable electronic structure, are arguably the most versatile functional dyes, with ample opportunities for tailored design via variations of both donor/acceptor (D/A) end groups and π-conjugated polymethine chain. A plethora spectral properties, such as strong solvatochromism, high polarizability hyperpolarizabilities, sensitizing capacity, motivates extensive studies applications in light-converting materials optoelectronics, nonlinear optics, optical storage, fluorescent probes, etc. Evidently, an understanding intrinsic structure-property relationships is a prerequisite successful dyes. For merocyanines, these regularities have been explored over 70 years, but only past three decades expanded beyond theory color solvatochromism toward structure ground excited states. This Review outlines fundamental principles, essential comprehension variable nature main emphasis on impact internal (chemical structure) external (intermolecular interactions) factors symmetry D-π-A chromophore. The research properties merocyanines different media reviewed context interplay virtual states: nonpolar polyene, ideal polymethine, zwitterionic polyene.

Language: Английский

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Visible light‐responsive azo‐based smart materials: Design, performance, and applications in energy storage

Smart Molecules, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Abstract Azobenzene and its derivatives are the most extensively investigated applied molecular photoswitches, which can undergo reversible transformation between trans cis isomers upon irradiation with light at specific wavelengths. Through structural geometry transformation, property alterations be integrated into smart materials to meet diverse application requirements. Most azo‐based photoswitches require UV for activation. However, complete activation within visible or even near‐infrared range could offer several benefits photoswitch applications, including improved biocompatibility, better penetration, enhanced solar utilization efficiency. This review presents an overview of development visible‐light responsive materials, covering design strategies their applications in energy storage. Recent efforts aimed enhancing performance storage highlighted. According different improving properties, these categorized as those that directly increase isomerization introduce phase transition energy. Furthermore, we discuss challenges opportunities this field a view inspire further exploration.

Language: Английский

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Exploration of Unconventional Excitation Wavelength and Dynamic Emission in Rare-Earth Doped Multilayer Core-Shell Structures: Application for Optical “Hard” and “Soft” Switching

Published: Jan. 1, 2024

Language: Английский

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