Photo- and Redox-Driven Artificial Molecular Motors

Chemical Reviews, Год журнала: 2019, Номер 120(1), С. 200 - 268

Опубликована: Авг. 15, 2019

Directed motion at the nanoscale is a central attribute of life, and chemically driven motor proteins are nature’s choice to accomplish it. Motivated inspired by such bionanodevices, in past few decades chemists have developed artificial prototypes molecular motors, namely, multicomponent synthetic species that exhibit directionally controlled, stimuli-induced movements their parts. In this context, photonic redox stimuli represent highly appealing modes activation, particularly from technological viewpoint. Here we describe evolution field photo- redox-driven provide comprehensive review work published 5 years. After an analysis general principles govern controlled directed movement scale, fundamental photochemical processes can enable its realization. The main classes light- motors illustrated, with particular focus on recent designs, thorough description functions performed these kinds devices according literature reports presented. Limitations, challenges, future perspectives critically discussed.

Язык: Английский

---

Advances in theE → ZIsomerization of Alkenes Using Small Molecule Photocatalysts

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2650 - 2694

Опубликована: Авг. 27, 2021

Geometrical E → Z alkene isomerization is intimately entwined in the historical fabric of organic photochemistry and enjoying a renaissance (Roth et al. Angew. Chem., Int. Ed. Engl. 1989 28, 1193–1207). This consequence fundamental stereochemical importance Z-alkenes, juxtaposed with frustrations thermal reactivity that are rooted microscopic reversibility. Accessing excited state paradigms allow this latter obstacle to be circumnavigated by exploiting subtle differences photophysical behavior substrate product chromophores: provides molecular basis for directionality. While direct irradiation operationally simple, photosensitization via selective energy transfer enables augmentation repertoire include substrates not directly photons. Through sustained innovation, an impressive portfolio tailored small molecule catalysts range triplet energies now widely available facilitate contra-thermodynamic thermo-neutral reactions generate Z-alkene fragments. review intended serve as practical guide covering geometric alkenes enabled catalysis from 2000 2020, logical sequel excellent treatment Dugave Demange (Chem. Rev. 2003 103, 2475–2532). The mechanistic foundations underpinning selectivity discussed together induction models rationales explain counterintuitive directionality these processes which very distinguish product. Implications subsequent stereospecific transformations, application total synthesis, regioselective polyene isomerization, spatiotemporal control pre-existing configuration broader sense discussed.

Язык: Английский

---

Molecular Imprinting: Materials Nanoarchitectonics with Molecular Information

Bulletin of the Chemical Society of Japan, Год журнала: 2018, Номер 91(7), С. 1075 - 1111

Опубликована: Апрель 13, 2018

Abstract Combining nanotechnology with other science disciplines is necessary to produce various materials nanoscale structural and functional information, which nanoarchitectonics, a novel paradigm create useful materials. One of the basic ideas in nanoarchitectonics use molecular-level information structurally design This strategy indeed used some existing fields technical realms. For example, molecular imprinting techniques provide possessing inside fabricated Revisiting this idea concept would have great meaning toward unification individual research into one key approach. In review, we survey fundamentals recent trends consideration nanoarchitectonics. Here, aspects examples are surveyed from advanced applications: (i) fundamental preparation polymers form nanoparticles, nanofibers, thin films, monolayers; (ii) surface coverage, post-modification, introduction new groups; (iii) imprinted controllable guest binding by external stimuli such as photo-responsive, temperature-sensitive, pH-sensitive, solvent-dependent, multi-stimuli responsive materials; (iv) using proteins template protein stamping; (v) cyclodextrins monomers; (vi) functions including highly sensitive selective sensors combined DNA aptamers enzymatic reactions, post-imprinting for sophisticated sensors, applications drug delivery systems.

Язык: Английский

---

Charge migration and charge transfer in molecular systems

Structural Dynamics, Год журнала: 2017, Номер 4(6)

Опубликована: Ноя. 1, 2017

The transfer of charge at the molecular level plays a fundamental role in many areas chemistry, physics, biology and materials science. Today, more than 60 years after seminal work R. A. Marcus, is still very active field research. An important recent impetus comes from ability to resolve ever faster temporal events, down attosecond time scale. Such high resolution now offers possibility unravel most elementary quantum dynamics both electrons nuclei that participate complex process transfer. This review covers research addresses following questions. Can we reconstruct migration across molecule on atomic length electronic scales? use strong laser fields control migration? temporally understand intramolecular dissociative ionization small molecules, transition-metal complexes conjugated polymers? tailor systems towards specific charge-transfer processes? What are scales steps liquids nanoparticles? Important new insights into each these topics, obtained state-of-the-art ultrafast spectroscopy and/or theoretical methods, summarized this review.

Язык: Английский

---

Molecular excited states through a machine learning lens

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(6), С. 388 - 405

Опубликована: Май 20, 2021

Язык: Английский

---

Future‐Oriented Advanced Diarylethene Photoswitches: From Molecular Design to Spontaneous Assembly Systems

Advanced Materials, Год журнала: 2021, Номер 34(16)

Опубликована: Дек. 6, 2021

Diarylethene (DAE) photoswitch is a new and promising family of photochromic molecules has shown superior performance as smart trigger in stimulus-responsive materials. During the past few decades, DAE achieved leap from simple to functional developed toward validity universal switching building block. In recent years, introduction into an assembly system been attractive strategy that enables behavior blocks be manifested at level entire system, beyond unit itself. This assembly-based will bring many unexpected results promote design manufacture generation advanced Here, advances fabrication diarylethene materials science, chemistry, biomedicine are reviewed.

Язык: Английский

---

Describing Chemical Reactivity with Frontier Molecular Orbitalets

JACS Au, Год журнала: 2022, Номер 2(6), С. 1383 - 1394

Опубликована: Июнь 16, 2022

Locality in physical space is critical understanding chemical reactivity the analysis of various phenomena and processes chemistry, biology, materials science, as exemplified concepts reactive functional groups active sites. Frontier molecular orbitals (FMOs) pinpoint locality bonds that are chemically because associated orbital energies thus have achieved great success describing reactivity, mainly for small systems. For large systems, however, delocalization nature canonical makes it difficult FMOs to highlight reactivity. To obtain localized also reflect frontier processes, we develop concept orbitalets (FMOLs) The was developed recently scaling correction method, which aims eliminating error common density approximations. Orbitalets both energy spaces contain information. FMOLs with highest among occupied lowest unoccupied ones. applications hexadeca-1,3,5,7,9,11,13,15-octaene its equilibrium geometry, inter- intra-molecular charge-transfer two transition states a bifurcating reaction demonstrate can connect quantum mechanical treatments systems reactivities by locating region Therefore, extend role describe insight, potentially broad applications.

Язык: Английский

---

Optical nanomaterials with focus on rare earth doped oxide: A Review

Materials Today Communications, Год журнала: 2021, Номер 27, С. 102277 - 102277

Опубликована: Март 27, 2021

Язык: Английский

---

Factors that Impact Photochemical Cage Escape Yields

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7379 - 7464

Опубликована: Май 14, 2024

The utilization of visible light to mediate chemical reactions in fluid solutions has applications that range from solar fuel production medicine and organic synthesis. These are typically initiated by electron transfer between a photoexcited dye molecule (a photosensitizer) redox-active quencher yield radical pairs intimately associated within solvent cage. Many these radicals undergo rapid thermodynamically favored "geminate" recombination do not diffuse out the cage surrounds them. Those escape useful reagents may subsequent important above-mentioned applications. process factors determine yields remain poorly understood despite decades research motivated their practical fundamental importance. Herein, state-of-the-art on light-induced appeared since seminal 1972 review J. P. Lorand entitled "The Cage Effect" is reviewed. This also provides some background for those new field discusses both homolytic bond photodissociation bimolecular induced reactions. concludes with key goals directions future promise elevate this very vibrant even greater heights.

Язык: Английский

---

From Fundamental Theories to Quantum Coherences in Electron Transfer

Journal of the American Chemical Society, Год журнала: 2018, Номер 141(2), С. 708 - 722

Опубликована: Ноя. 9, 2018

Photoinduced electron transfer (ET) is a cornerstone of energy transduction from light to chemistry. The past decade has seen tremendous advances in the possible role quantum coherent effects light-initiated and ET processes chemical, biological, materials systems. prevalence such coherence holds promise increase efficiency robustness transport even face energetic or structural disorder. A primary motive this Perspective work out how think about "coherence" reactions. We will discuss interplay basic parameters governing reactions—like electronic coupling, interactions with environment, intramolecular high-frequency vibrations—impact coherences. This includes revisiting insights seminal on theory time-resolved measurements dynamics explore coherences conclude by suggesting that addition optical spectroscopies, validating functional would require simultaneous mapping correlated motion atomically resolved nuclear structure.

Язык: Английский

---