Photochromic Molecular Switches Research Articles

Revisiting photocyclization of the donor-acceptor stenhouse adduct: missing pieces in the mechanistic jigsaw discovered.

Donor-acceptor Stenhouse adducts (DASA) have recently emerged as a class of visible-light-induced photochromic molecular switches, but their photocyclization mechanism remains puzzling and incomplete. In this work, we carried out MS-CASPT2//SA-CASSCF calculations to reveal the complete mechanism of the dominant channels and possible side reactions. We found that a new thermal-then-photo isomerization channel, i.e., EEZ → EZZ → EZE, other than the commonly accepted EEZ → EEE → EZE channel, is dominant in the initial step. Besides, our calculations rationalized why the expected byproducts ZEZ and ZEE are unobserved and proposed a competitive stepwise channel for the final ring-closure step. The findings here redraw the mechanistic picture of the DASA reaction by better accounting for experimental observations, and more importantly, provide critical physical insight in understanding the interplay between thermal- and photo-induced processes widely present in photochemical synthesis and reactions.

Excited-state resonance Raman spectroscopy probes the sequential two-photon excitation mechanism of a photochromic molecular switch.

Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400nm. Many of the modes that become enhanced in the 750nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation.

Designs and Applications of Multi-stimuli Responsive FRET Processes in AIEgen-Functionalized and Bi-fluorophoric Supramolecular Materials

Materials capable of displaying strong ratiometric fluorescence with Förster resonance energy transfer (FRET) processes have attracted much research interest because of various chemosensor and biomedical applications. This review highlights several popular strategies in designing FRET-OFF/ON mechanisms of ratiometric fluorescence systems. In particular, the developments of organic and polymeric FRET materials featuring aggregation-induced emission-based luminogens (AIEgens), supramolecular assemblies, photochromic molecular switches and surfactant-induced AIE/FRET mechanisms are presented. AIEgens have been frequently employed as FRET donor and/or acceptor fluorophores to obtain enhanced ratiometric fluorescences in solution and solid states. Since AIE effects and FRET processes rely on controllable distances between fluorophores, many interesting fluorescent properties can be designed by regulating aggregation states in polymers and supramolecular systems. Photo-switchable fluorophores, such as spiropyran and diarylethene, provide drastic changes in fluorescence spectra upon photo-induced isomerizations, leading to photo-switching mechanisms to activate/deactivate FRET processes. Supramolecular assemblies offer versatile platforms to regulate responsive FRET processes effectively. In rotaxane structures, the donor-acceptor distance and FRET efficiency can be tuned by acid/base-controlled shuttling of the macrocycle component. The tunable supramolecular interactions are strongly influenced by external factors (such as pH values, temperatures, analytes, surfactants, UV-visible lights, etc.), which induce the assembly and disassembly of host-guest systems and thus their FRET-ON/FRET-OFF behavior. In addition, the changes in donor or acceptor fluorescence profiles upon detections of analytes can also sufficiently alter the FRET behavior and result in different ratiometric fluorescence outputs. The strategies and examples provided in this review offer the insights and toolkits for future FRET-based material developments.

Wide-range IR spectra of diarylethene derivatives and their simulation using the density functional theory

Diarylethenes (DAEs), promising photochromic molecular switches, undergo pericyclic reactions upon ultraviolet or visible light illumination. For this reason, most studies on DAEs employ UV–vis spectroscopies. However, also their infrared (IR) spectra are valuable, in particular, for understanding the vibrational dynamics which accompanies the relevant photoreactions. An accurate assignment of IR bands to molecular modes can be achieved through a comparison between experimental and computed theoretical spectra. Even though more sophisticated computational methods are available, the density functional theory (DFT) is usually employed for this task, because of its modest cost and versatility. Here, we have tested the ability of several DFT functionals to reproduce the wide-range, 400–3200 cm−1, IR spectra of open and closed isomers of four representative DAE molecules. We find that global and range-separated, corrected for anharmonicity by scaling factors, hybrid DFT functionals are able to reproduce the IR spectra of DAEs, however, instead of the popular B3LYP functional we propose the use of the dispersion-corrected PBE0 functional. The paper also proposes a semi-automatic method of band assignment.

Acid-, mechano- and photochromic molecular switches based on a spiropyran derivative for rewritable papers

In this work, we report a novel acid-, photo- and mechanochromic material based on a spiropyran (SP) derivative.

Strategies for Incorporating Graphene Oxides and Quantum Dots into Photoresponsive Azobenzenes for Photonics and Thermal Applications.

Graphene represents a new generation of materials which exhibit unique physicochemical properties such as high electron mobility, tunable optics, a large surface to volume ratio, and robust mechanical strength. These properties make graphene an ideal candidate for various optoelectronic, photonics, and sensing applications. In recent years, numerous efforts have been focused on azobenzene polymers (AZO-polymers) as photochromic molecular switches and thermal sensors because of their light-induced conformations and surface-relief structures. However, these polymers often exhibit drawbacks such as low photon storage lifetime and energy density. Additionally, AZO-polymers tend to aggregate even at moderate doping levels, which is detrimental to their optical response. These issues can be alleviated by incorporating graphene derivatives (GDs) into AZO-polymers to form orderly arranged molecules. GDs such as graphene oxide (GO), reduced graphene oxide (RGO), and graphene quantum dots (GQDs) can modulate the optical response, energy density, and photon storage capacity of these composites. Moreover, they have the potential to prevent aggregation and increase the mechanical strength of the azobenzene complexes. This review article summarizes and assesses literature on various strategies that may be used to incorporate GDs into azobenzene complexes. The review begins with a detailed analysis of structures and properties of GDs and azobenzene complexes. Then, important aspects of GD-azobenzene composites are discussed, including: (1) synthesis methods for GD-azobenzene composites, (2) structure and physicochemical properties of GD-azobenzene composites, (3) characterization techniques employed to analyze GD-azobenzene composites, and most importantly, (4) applications of these composites in various photonics and thermal devices. Finally, a conclusion and future scope are given to discuss remaining challenges facing GD-azobenzene composites in functional science engineering.

Spiropyran-Based Drug Delivery Systems.

Nanocarriers are rapidly growing in popularity in the field of drug delivery. The ability of nanocarriers to encapsulate and distribute poorly soluble drugs while minimising their undesired effects is significantly advantageous over traditional drug delivery. Nanocarriers can also be decorated with imaging moieties and targeting agents, further incrementing their functionality. Of recent interest as potential nanocarriers are spiropyrans; a family of photochromic molecular switches. Due to their multi-responsiveness to endo- and exogenous stimuli, and their intrinsic biocompatibility, they have been utilised in various drug delivery systems (DDSs) to date. In this review, we provide an overview of the developments in spiropyran-based DDSs. The benefits and drawbacks of utilising spiropyrans in drug delivery are assessed and an outline of spiropyran-based drug delivery systems is presented.

An AIE-active dual fluorescent switch with negative photochromism for information display and encryption

A negative photochromic molecular switch with AIE and two-color fluorescence conversion properties was synthesized.

New Insight on Photoisomerization Kinetics of Photo-Switchable Thin Films Based on Azobenzene/Graphene Hybrid Additives in Polyethylene Oxide

In this work, we reported a new insight on the kinetics of photoisomerization and time evolution of hybrid thin films considering the azo-dye methyl red (MR) incorporated with graphene accommodated in polyethylene oxide (PEO). The kinetics of photoisomerization and time-evolution of hybrid thin films were investigated using UV-Vis s and FTIR spectroscopies, as well as appropriate models developed with new analytical methods. The existence of azo-dye MR in the complex is crucial for the resource action of the trans cis cycles through UV-illumination Visible-illumination relaxations. The results of the UV–Vis and the FTIR investigations prove the cyclical trans cis-states. Consequently, PEO-(MR-Graphene) hybrid composite thin films can be introduced as possible applicants for photochromic molecular switches, light-gated transistors, and molecular solar thermal energy storage media.

Fluorescent Photochromic α‐Cyanodiarylethene Molecular Switches: An Emerging and Promising Class of Functional Diarylethene

AbstractFluorescent photochromic molecules that exhibit distinct light‐triggered changes in their emission colors are highly desirable for the fabrication of smart soft materials and advanced photonic devices. α‐Cyanodiarylethenes, that is, α‐cyano‐functionalized diarylethenes, as alternative “non‐azo” Z/E photochromic molecular switches, are popular choices due to their unique characteristics such as their aggregation‐induced emission or aggregation‐induced‐enhanced emission behavior in their self‐assembled states, and visible changes in fluorescence colors during Z/E photoisomerization. In recent years, the development of fluorescent photochromic α‐cyanodiarylethene‐based compounds including α‐cyanostilbenes, dicyanodistyrylbenzenes, and diaryldicyanoethenes, has mainly focused on molecular design, photochemical and photophysical behavior in solution, and smart soft matter technologies. In this review, recent significant achievements in light‐responsive systems based on the Z/E photoisomerization of fluorescent photochromic α‐cyanodiarylethene switches that span the range from liquid crystals to gels and finally to self‐assembled nanostructures, are highlighted. The smart soft materials constructed from α‐cyanodiarylethene molecular switches find use in a plethora of areas, including display, sensing, encrypting, actuating, and biomedical imaging applications, among others. The review concludes with a brief perspective on some major challenges and opportunities for the future development of light‐responsive smart soft photonic materials.

Solid-state photochromic molecular switches based on axially chiral and helical spiropyrans

Solid-state photochromic switches with reversible luminescence modulation property have wide applications in optical data storage, anticounterfeiting, sensing, and bioimaging, however, it is a significant challenge to design and prepare such materials. In the present work, a novel class of chiral and helical binaphthyl-substituted spiropyrans has been synthesized and characterized. The introduction of binaphthyl can not only promote the solid-state luminescence but also achieve the interesting chiroptical switching properties for the potential applications in chiral recognition and circularly polarized luminescence. The single-crystal structures and density functional theory calculations reveal that the presence of strong electron-withdrawing nitro groups can promote photoswitch efficiency by stabilizing the electron-rich conjugated merocyanine with the lower electron cloud density and LUMO/HOMO levels. For charge transfer in excited states, π → π* transition would enhance emission, but n → π* transition and intramolecular charge transfer show the opposite effect. Therefore, these photochromic switches provide a novel paradigm in the design of multiple-responsive, chiral, and luminescent materials.

Self-regulating photochemical Rayleigh-B\xe9nard convection using a highly-absorbing organic photoswitch

We identify unique features of a highly-absorbing negatively photochromic molecular switch, donor acceptor Stenhouse adduct (DASA), that enable its use for self-regulating light-activated control of fluid flow. Leveraging features of DASA’s chemical properties and solvent-dependent reaction kinetics, we demonstrate its use for photo-controlled Rayleigh-Bénard convection to generate dynamic, self-regulating flows with unparalleled fluid velocities (~mm s−1) simply by illuminating the fluid with visible light. The exceptional absorbance of DASAs in solution, uniquely controllable reaction kinetics and resulting spatially-confined photothermal flows demonstrate the ways in which photoswitches present exciting opportunities for their use in optofluidics applications requiring tunable flow behavior.

Design of Collective Motions from Synthetic Molecular Switches, Rotors, and Motors.

Precise control over molecular movement is of fundamental and practical importance in physics, biology, and chemistry. At nanoscale, the peculiar functioning principles and the synthesis of individual molecular actuators and machines has been the subject of intense investigations and debates over the past 60 years. In this review, we focus on the design of collective motions that are achieved by integrating, in space and time, several or many of these individual mechanical units together. In particular, we provide an in-depth look at the intermolecular couplings used to physically connect a number of artificial mechanically active molecular units such as photochromic molecular switches, nanomachines based on mechanical bonds, molecular rotors, and light-powered rotary motors. We highlight the various functioning principles that can lead to their collective motion at various length scales. We also emphasize how their synchronized, or desynchronized, mechanical behavior can lead to emerging functional properties and to their implementation into new active devices and materials.

Experimental and computational electrochemistry of quinazolinespirohexadienone molecular switches - differential electrochromic vs photochromic behavior.

Our undergraduate research group has long focused on the preparation and investigation of electron-deficient analogs of the perimidinespirohexadienone (PSHD) family of photochromic molecular switches for potential application as "photochromic photooxidants" for gating sensitivity to photoinduced charge transfer. We previously reported the photochemistry of two closely related and more reducible quinazolinespirohexadienones (QSHDs), wherein the naphthalene of the PSHD is replaced with a quinoline. In the present work, we report our investigation of the electrochemistry of these asymmetric QSHDs. In addition to the short wavelength and photochromic long-wavelength isomers, we have found that a second, distinct long-wavelength isomer is produced electrochemically. This different long-wavelength isomer arises from a difference in the regiochemistry of spirocyclic ring-opening. The structures of both long-wavelength isomers were ascertained by cyclic voltammetry and 1H NMR analyses, in concert with computational modeling. These results are compared to those for the symmetric parent PSHD, which due to symmetry possesses only a single possible regioisomer upon either electrochemical or photochemical ring-opening. Density functional theory calculations of bond lengths, bond orders, and molecular orbitals allow the rationalization of this differential photochromic vs electrochromic behavior of the QSHDs.

Photoswitchable Fluorescent Liquid Crystal Nanoparticles and Their Inkjet‐Printed Patterns for Information Encrypting and Anti‐Counterfeiting

AbstractLiquid crystal nanoparticles (LCNPs) with desirable multifunctionality are catching increasing attention due to their promising applications in various fields. However, reversible photoswitchable fluorescent LCNPs are not reported until now. Here, the first example of water‐dispersible, reversibly phototunable fluorescent LCNPs prepared through a miniemulsion polymerization technique is presented. The LCNPs mainly consist of an aggregation‐induced emission enhancement (AIEE)‐active dicyanodistyrylbenzene‐based monomer, a LC cross‐linking monomer, and a dithienylethene (DAE) derivative as a photochromic molecular switch. The fluorescence of the resultant LCNPs can be switched reversibly between bright (ON) and dark (OFF) states with a high contrast and excellent repeatability upon alternating irradiation of 365 nm UV light and visible light (λ > 450 nm). This observation could be attributed to ring‐opening/ring‐closing photoisomerization of the DAE structure on the basis of an intraparticle fluorescence resonance energy transfer process between the AIEE‐active monomer and DAE derivative. More importantly, the potential for aqueous dispersion of the photoswitchable fluorescent LCNPs as a security ink for information encryption and anti‐counterfeiting is further demonstrated. The results demonstrate that the reversible photoswitchable fluorescent LCNPs as multifunctional nanomaterials exhibit promising applications in photonic fields.

Unsymmetrical photochromic bithienylethene-bridge tetraphenylethene molecular switches: Synthesis, aggregation-induced emission and information storage

Aggregation-induced emission (AIE) active photochromic molecules have attracted growing attention for their versatile applications. Here we designed and synthesized five newly unsymmetrical photochromic diarylethene (DAE) dyads (BTE1–5) by connecting tetraphenylethene (TPE) and aromatic substituent via bithienylethene (BTE) bridge. The chemical structures of those compounds were identified by 1H NMR, 13C NMR and HRMS. The absorption and emission of these dyads were investigated by UV–vis and fluorescence spectroscopy, respectively. The results showed that all those compounds exhibited typically AIE or aggregation-induced emission enhancement (AIEE) characteristic. Particularly, when an aggregation-caused quenching (ACQ) fluorophore (triphenylamine) was grafted to the molecule, connecting with TPE via BTE-bridge, the ACQ phenomenon was dissipated and converted to an AIE luminophore, and those compounds exhibited photochromism upon irradiation with alternative UV and visible light. The solution or solid of those compounds showed distinctly fluorescence switching “ON” or “OFF” observation upon irradiation with alternative UV and visible light. It is interesting that BTE1 could be applied in recording and rewritable information storage, and the cyclization quantum yields could be affected by substituent significantly.

Theoretical insights into the effect of heterocycles of the molecular framework on photochromic magnetic properties of diarylethene compounds

AbstractConsidering the effect of heterocycles on photochromic magnetic properties, we presented a comparative study among series of closed‐ and open‐ring isomers of benzothiophene‐, benzofuran‐, and 1‐methylindole‐based diarylperfluorocyclopentenes or diarylmaleic anhydrides bearing nitronyl nitroxide diradicals. Owing to the better itinerant exchange of the unpaired electrons for the closed‐ring isomers than for the open‐ring ones, the former have ferromagnetic coupling interactions, while the later are antiferromagnetic. This difference indicates that the interconversion between them is switchable. In the molecular framework of the diarylethene, the participation of benzofuran group(s) can increase Jab value and contributes to thermal stability, while that of 1‐methylindole group(s) can increase Jab value and has block effect on thermal stability. Still, the later can lead to red‐shift of the maximum absorption wavelength, which is benefit for the requirement of the application to optical memory media. It is the better choice for perfluorocyclopentenes than for maleic anhydrides as the bridging group in construction of photochromic magnetic molecular switch of diarylethene compound.

Preserving \u03c0-conjugation in covalently functionalized carbon nanotubes for optoelectronic applications

Covalent functionalization tailors carbon nanotubes for a wide range of applications in varying environments. Its strength and stability of attachment come at the price of degrading the carbon nanotubes sp2 network and destroying the tubes electronic and optoelectronic features. Here we present a non-destructive, covalent, gram-scale functionalization of single-walled carbon nanotubes by a new [2+1] cycloaddition. The reaction rebuilds the extended π-network, thereby retaining the outstanding quantum optoelectronic properties of carbon nanotubes, including bright light emission at high degree of functionalization (1 group per 25 carbon atoms). The conjugation method described here opens the way for advanced tailoring nanotubes as demonstrated for light-triggered reversible doping through photochromic molecular switches and nanoplasmonic gold-nanotube hybrids with enhanced infrared light emission.

Visualizing Excited-State Dynamics of a Diaryl Thiophene: Femtosecond Stimulated Raman Scattering as a Probe of Conjugated Molecules.

Conjugated organic polymers based on substituted thiophene units are versatile building blocks of many photoactive materials, such as photochromic molecular switches or solar energy conversion devices. Unraveling the different processes underlying their photochemistry, such as the evolution on different electronic states and multidimensional structural relaxation, is a challenge critical to defining their function. Using femtosecond stimulated Raman scattering (FSRS) supported by quantum chemical calculations, we visualize the reaction pathway upon photoexcitation of the model compound 2-methyl-5-phenylthiophene. Specifically, we find that the initial wavepacket dynamics of the reaction coordinates occurs within the first ≈1.5 ps, followed by a ≈10 ps thermalization. Subsequent slow opening of the thiophene ring through a cleavage of the carbon-sulfur bond triggers an intersystem crossing to the triplet excited state. Our work demonstrates how a detailed mapping of the excited-state dynamics can be obtained, combining simultaneous structural sensitivity and ultrafast temporal resolution of FSRS with the chemical information provided by time-dependent density functional theory calculations.

Blue to near-IR energy transfer cascade within a dye-doped polymer matrix, mediated by a photochromic molecular switch.

The spectroscopic properties of a poly(methyl methacrylate) matrix doped with a coumarin dye, a cyanine dye, and a photochromic spiropyran dye have been investigated. Before UV irradiation of the matrix, excitation of the coumarin dye results in minimal energy transfer to the cyanine dye. The energy transfer is substantially enhanced following UV irradiation of the matrix, which converts the colourless spiropyran isomer to the coloured merocyanine isomer, which then acts as an intermediate bridge by accepting energy from the coumarin dye and then donating energy to the cyanine dye. This demonstration of a switchable energy transfer cascade should help initiate new research directions in molecular photonics.