Two-way photoswitching using one type of near-infrared light, upconverting nanoparticles, and changing only the light intensity (original) (raw)
Related papers
The use of upconverting nanoparticles to drive organic photoreactions
One of the primary disadvantages of organic photochemistry is the need for high-energy UV light, light that has many detrimental qualities. A viable solution to this problem is the use of upconverting nanoparticles (UCNP) that can locally convert near infrared (NIR) laser light into UV light or visible light of sufficient energy to drive organic photoreactions.
Photoswitching of bis-spiropyran using near-infrared excited upconverting nanoparticles
Chemical Communications, 2012
Thulium oxide (Tm 2 O 3 , 99.99+ %), ytterbium oxide (Yb 2 O 3 , 99.99%), yttrium oxide (Y Y 2 O 3 , 99.99+ %), triflouroacetic acid (CF 3 COOH, 99%), lithium trifluoroacetate (CF 3 COOLi, 98%), oleic acid (technical grade, 90%), and 1-octadecene (technical grade, 90%) were all purchased from Sigma-Aldrich and were used without further purification. LiYF 4 :Tm 3+ , Yb 3+ UCNPs were synthesized via the thermal decomposition method previously demonstrated by our group 1-3 , which was comprised of a two-step process. In the first step, a 10 mL mixture of water/trifluoroacetic acid (1:1) was added to a
Near-Infrared to Visible Light-Upconversion in Molecules: From Dream to Reality
The Journal of Physical Chemistry C, 2013
Light-upconversion via stepwise energy transfer from a sensitizer to an activator exploits linear optics for converting low-energy infrared or near-infrared incident photons to higher energy emission. This approach is restricted to activators possessing intermediate long-lived excited states such as those found for trivalent lanthanide cations dispersed in solid-state matrices. When the activator is embedded in a molecular complex, efficient nonradiative relaxation processes usually reduce excited state lifetimes to such an extent that upconversion becomes too inefficient to be detected under practical excitation intensities. Theoretical considerations presented here predict that the combination of at least two millisecond time scale sensitizers with a central lanthanide activator in supramolecular complexes circumvents this bottleneck by creating a novel upconversion pathway, in which successive excitations are stored on the sensitizers prior to inducing stepwise energy transfer processes. Application of this concept to the chromium/erbium pair demonstrates that strong-field trivalent chromium chromophores irradiated with near-infrared photons produce upconverted green erbium-centered emission in discrete dinuclear and trinuclear triple-stranded helicates.
Light-induced reversible switching of generation and extinction of an organic radical anion
2024
Radicals play a crucial role across various domains, ranging from serving as catalysts in chemical reactions to materials for spintronic applications. Currently, a major challenge for the chemists is the development of the next generation of organic radicals controllable by photons. To tackle this challenge, here we introduce a dyad system that combines a dimethyldihydropyrene (DHP) photochromic unit with a naphthalene diimide (NDI) moiety. This system forms a stable organic NDI-based radical-anion upon exposure to light in a solvent containing a small amount of an amine that acts as an electron donor. The radical anion formtion has also been demonstrated with chemical reductant. The photoisomerization of this photochromic system converts it into a less-conjugated and less-electron-rich form, affecting the generation of the radical as well as its stability. Consequently, light-induced isomerization effectively quenches the radical. Thus, the formation and existence of the radical can be adjusted by manipulating the photoisomerization of the photochromic unit under diverse light sources. Additionally, the system exhibits significant differences in emission in the radical and the closed-shell state, thereby offering a dual readout of the state of the molecule.
Theoretical Chemistry Accounts, 2007
In recent years, computational photochemistry has become a valid tool for the investigation of photophysical properties and photochemical reaction mechanisms in organic chromophores. Theoretical chemists can now adapt their tools to the subject under investigation and to the type and accuracy of the desired information. Different computational strategies can now be adopted to characterize different aspects of the photoinduced molecular reactivity of a given chromophore and to provide, in principle, a quite detailed description of the reactive process from energy absorption to photoproducts formation. A basic aim is to establish a correlation between the structure of the molecule and its photochemical outcome, and, in particular, to assess the effect of modifications of the chromophore and of the molecular environment. In this perspective recent advances and applications of photoinduced cis trans isomerizations involving some organic chromophores active in biologically or technologically relevant problems is reviewed here and discussed in the light of new results. In particular, the photochemistry of azobenzene, retinals and of the green fluorescent protein chromophore is considered, taking into account structural changes and environment effects. The results presented in this work are intended to be a first step toward the design of chromophores that can act as molecular photoswitches.
Photochemical & Photobiological Sciences, 2010
Y. Ishibashi, K. Okuno, C. Ota et al., Photochem. Photobiol. Sci., 2010, 9, 172 Probing photochromic properties by correlation of UV-visible and infra-red absorption spectroscopy: a case study with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene A. Spangenberg, J. A. Piedras Perez, A. Patra et al., Photochem. Photobiol. Sci., 2010, 9, 188 The DC gate in Channelrhodopsin-2: crucial hydrogen bonding interaction between C128 and D156 M. Nack, I. Radu, M. Gossing et al., Photochem. Photobiol. Sci., 2010, 9, 194 Quantitative investigations of cation complexation of photochromic 8-benzothiazole-substituted benzopyran: towards metal-ion sensors M. I. Zakharova, C. Coudret, V. Pimienta et al., Photochem. Photobiol. Sci., 2010, 9, 199 Spiropyrans as molecular optical switches B. Seefeldt, R. Kasper, M. Beining et al., Photochem. Photobiol. Sci., 2010, 9, 213 Photoinduced shape changes of diarylethene single crystals: correlation between shape changes and molecular packing L. Kuroki, S. , K. Yoza, M. Morimoto and M. Irie, Photochem. Photobiol. Sci., 2010, 9, 221 Functional interaction structures of the photochromic retinal protein rhodopsin K. Kirchberg, T.-Y. Kim, S. Haase and U. Alexiev, Photochem. Photobiol. Sci., 2010, 9, 226 Facile synthesis and characterization of new photochromic trans-dithienylethenes functionalized with pyridines and fluorenes Q. Luo, Y. Liu, X. Li and H. Tian, Photochem. Photobiol. Sci., 2010, 9, 234
Biosensors, 2019
Lanthanide-doped upconverting nanoparticles (UCNP) are being extensively studied for bioapplications due to their unique photoluminescence properties and low toxicity. Interest in RET applications involving UCNP is also increasing, but due to factors such as large sizes, ion emission distributions within the particles, and complicated energy transfer processes within the UCNP, there are still many questions to be answered. In this study, four types of core and core-shell NaYF4-based UCNP co-doped with Yb3+ and Tm3+ as sensitizer and activator, respectively, were investigated as donors for the Methyl 5-(8-decanoylbenzo[1,2-d:4,5-d′]bis([1,3]dioxole)-4-yl)-5-oxopentanoate (DBD-6) dye. The possibility of resonance energy transfer (RET) between UCNP and the DBD-6 attached to their surface was demonstrated based on the comparison of luminescence intensities, band ratios, and decay kinetics. The architecture of UCNP influenced both the luminescence properties and the energy transfer to th...
Scientific Reports
Lanthanide-based, spectrally shifting, and multi-color luminescent upconverting nanoparticles (UCNPs) have received much attention in the last decades because of their applicability as reporter for bioimaging, super-resolution microscopy, and sensing as well as barcoding and anti-counterfeiting tags. A prerequisite for the broad application of UCNPs in areas such as sensing and encoding are simple, robust, and easily upscalable synthesis protocols that yield large quantities of UCNPs with sizes of 20 nm or more with precisely controlled and tunable physicochemical properties from low-cost reagents with a high reproducibility. In this context, we studied the reproducibility, robustness, and upscalability of the synthesis of β-NaYF4:Yb, Er UCNPs via thermal decomposition. Reaction parameters included solvent, precursor chemical compositions, ratio, and concentration. The resulting UCNPs were then examined regarding their application-relevant physicochemical properties such as size, si...
The role of asymmetry on the photoisomerization of dithienylethene molecule photoswitch
2022
Dithienylethene (DTE) molecular photoswitches have shown to be excellent candidates in the design of efficient optoelectronic devices, due to their high photoisomerization quantum yield (QY), for which symmetry is suggested to play a crucial role. Here, we present a theoretical study on the photochemistry of a non-symmetric dithienylethene photoswitch, with a special emphasis on the effect of asymmetric substitution on the photocyclization and photoreversion mechanisms. We used the Spin-Flip Time Dependent Density Functional Theory (SF-TDDFT) method to locate and characterize the main structures (conical intersections and minima) of the ground state and the first two excited states, S 1 and S 2 , along the ring-opening/closure reaction coordinate of the photocyclization and photoreversion processes, and to identify the important coordinates governing the radiationless decay pathways. Our results suggest that while the main features that characterize the photoisomerization of symmetric DTEs are also present for the photoisomerization of the non-symmetric DTE, the lower energy barrier on S 1 along the cycloreversion reaction speaks in favor of a more efficient and therefore a higher cycloreversion QY for the nonsymmetric DTEs, making them a better candidate for molecular optoelectronic devices than their symmetric counterparts.