Breaking the photoswitch speed limit.

The forthcoming generation of materials, including artificial muscles, recyclable and healable systems, photochromic heterogeneous catalysts, or tailorable supercapacitors, relies on the fundamental concept of rapid switching between two or more discrete forms in the solid state. Herein, we report a breakthrough in the "speed limit" of photochromic molecules on the example of sterically-demanding spiropyran derivatives through their integration within solvent-free confined space, allowing for engineering of the photoresponsive moiety environment and tailoring their photoisomerization rates. The presented conceptual approach realized through construction of the spiropyran environment results in ~1000 times switching enhancement even in the solid state compared to its behavior in solution, setting a record in the field of photochromic compounds. Moreover, integration of two distinct photochromic moieties in the same framework provided access to a dynamic range of rates as well as complementary switching in the material's optical profile, uncovering a previously inaccessible pathway for interstate rapid photoisomerization.

Non-Conjugated Bis-(Dithienylethene)-Naphthalenediimide as a Dynamic Anti-Counterfeiting Agent: Driving the Wheel of Photoswitching Enactment.

Photochromic fluorescent molecules dramatically extend their fields of applications ranging from optical memories, bioimaging, photoswitches, photonic devices, anti-counterfeiting technology and many more. Here, we have logically designed and synthesized a triazole appended bis-(dithienylethene)-naphthalenediimide based photo-responsive material, 5, which demonstrated fluorescence enhancement property upon photocyclization (ΦF =0.42), with high photocyclization (44 s, ksolution =0.0355 s-1 , ksolid =0.0135 s-1 ) and photocycloreversion (160 s, ksolution =0.0181 s-1 , ksolid =0.0085 s-1 ) rate and decent photoreaction quantum yield (Φo→c =0.93 and Φc→o =0.11). The open isomer almost converted to the closed isomer at photo-stationary state (PSS) with distinct color change from colorless to blue with 92.85 % conversion yield. A reversible noninvasive modulation of fluorescence through efficient photoinduced electron transfer (PET) process was observed both in solution as well as in solid state. The fluorescence modulation through PET process was further corroborated with thermodynamic calculations using the Rehm-Weller equation and quantum chemical studies (DFT). The thermally stable compound 5 exhibits high fatigue resistance property (up to 50 cycles) both in solution and solid state. Furthermore, the compound 5 was successfully applied as erasable ink and in deciphering secret codes (Quick Response/bar code) portending potential promising application in anti-counterfeiting.

Preparation of 5-(Acyloxymethyl)furfurals from Carbohydrates Using Zinc Chloride/Acetic Acid Catalyst System and Their Synthetic Value Addition.

5-(Acyloxymethyl)furfurals (AMFs) have received considerable attention as hydrophobic, stable, and halogen-free congeners of 5-(hydroxymethyl)furfural (HMF) for synthesizing biofuels and biochemicals. In this work, AMFs have been prepared directly from carbohydrates in satisfactory yields using the combination of ZnCl2 as the Lewis acid catalyst and carboxylic acid as the Brønsted acid catalyst. The process was initially optimized for 5-(acetoxymethyl)furfural (AcMF) and then extended to producing other AMFs. The effects of reaction temperature, duration, loading of the substrate, and dosage of ZnCl2 on AcMF yield were explored. Fructose and glucose provided AcMF in 80% and 60% isolated yield, respectively, under optimized parameters (5 wt % substrate, AcOH, 4 equiv ZnCl2, 100 °C, 6 h). Finally, AcMF was converted into high-value chemicals, such as 5-(hydroxymethyl)furfural, 2,5-bis(hydroxymethyl)furan, 2,5-diformylfuran, levulinic acid, and 2,5-furandicarboxylic acid in satisfactory yields to demonstrate the synthetic versatility of AMFs as carbohydrate-derived renewable chemical platforms.

Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System.

The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (Φo→c) and photocycloreversion (Φc→o) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (Φo→c) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.

Oxidation-Induced Differentially Selective Turn-On Fluorescence via Photoinduced Electron Transfer Based on a Ferrocene-Appended Coumarin-Quinoline Platform: Application in Cascaded Molecular Logic.

Differentially selective molecular sensors that exhibit differential response toward multiple analytes are cost-effective and in high demand for various practical applications. A novel, highly differentially selective electrochemical and fluorescent chemosensor, 5, based on a ferrocene-appended coumarin-quinoline platform has been designed and synthesized. Our designed probe is very specific toward Fe3+ via a reversible redox process, whereas it detects Cu2+ via irreversible oxidation. Interestingly, it exhibits differential affinity toward the Cu+ ion via complexation. High-resolution mass spectrometry, 1H NMR titration, and IR spectral studies revealed the formation of a bidentate Cu+ complex involving an O atom of the amide group attached to the quinoline ring and a N atom of imine unit, and this observation was further supported by quantum-chemical calculations. The metal binding responses were further investigated by UV-vis, fluorescence spectroscopy, and electrochemical analysis. Upon the addition of Fe3+ and Cu2+ ions, the fluorescence emission of probe 5 shows a "turn-on" signal due to inhibition of the photoinduced electron transfer (PET) process from a donor ferrocene unit to an excited-state fluorophore. The addition of sodium l-ascorbate (LAS) as a reducing agent causes fluorescence "turn off" for the Fe3+ ion because of reemergence of the PET process but not for the Cu2+ ion because it oxidizes the ferrocene unit to a ferrocenium ion with its concomitant reduction to Cu+, which further complexes with 5. Thermodynamic calculations using the Weller equation along with density functional theory calculations validate the feasibility of the PET process. A unique combination of Fe3+, LAS, and Cu2+ ions has been used to produce a molecular system demonstrating combinational "AND-OR" logic operation.