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

Abstract

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.

Ferrocene–Dithienylethene–Naphthalenediimide-Based Multifunctional Molecular Switch: Applications in Anticounterfeiting and Controlled Singlet Oxygen Generation

“…Apart from fluorescence switching, the control of speed of photoswitching in the presence of light is also a basic requirement to get a highly efficient photoswitch. 22 In this regard, conjugated way of attachment generally restricts the photoswitching speed, 23 whereas nonconjugated combination between the cNDI, DTE, and ferrocene units may impart high-speed switching between the two isomeric states with good photoisomerization quantum yields. 24 Herein, we have developed a Fc-DTE-cNDI triad, with unique multifunctional switching capability using photochromic and redox tunable properties.…”