Reversible Photomodulation of Electronic Communication in a π‐Conjugated Photoswitch‐Fluorophore Molecular Dyad

Abstract

The extent of electronic coupling between a boron dipyrromethene (BODIPY) fluorophore and a diarylethene (DAE) photoswitch has been modulated in a covalently linked molecular dyad by irradiation with either UV or visible light. In the open isomer, both moieties can be regarded as individual chromophores, while in the closed form the lowest electronic (S0 →S1 ) transition of the dyad is slightly shifted, enabling photomodulation of its fluorescence. Transient spectroscopy confirms that the dyad behaves dramatically different in the two switching states: while in the open isomer it resembles an undisturbed BODIPY fluorophore, in the closed isomer no fluorescence occurs and instead a red-shifted DAE behavior prevails.

Theoretical study on the reaction mechanism of the thermal cis–trans isomerization of fluorine-substituted azobenzene derivatives

“…Molecular photoswitches have aroused widespread interest in recent years. [1][2][3][4][5] Because of their unique photochromic characteristics, 6 they have been widely used in molecular data storage, 7-9 photopharmacology, 10 optochemical genetics, 11 materials science, 12 and biomolecules 13,14 among other areas. Over the past few decades, most research has been focused on azobenzenes, 15 spiropyrans, 16 diarylethenes, 17 and stilbenes 18 which are all characterized by photoisomerization.…”

Modulation of Eu(III) and Yb(III) Luminescence Using a DTE Photochromic Ligand

“…Although DTE can be a fluorescent switch itself, 29,30 it serves as a non-fluorescent switch to modulate the fluorescence of a neighboring fluorophore through FRET as mentioned above, including in combinations of DTE and metal centers that have opened up new perspectives for the design of metal based photoswitchable fluorescent materials. [31][32][33][34][35][36][37][38][39][40][41][42][43] A c c e p t e d m a n u s c r i p t Among all fluorophores, lanthanide occupy a very particular place due to their unique photophysical properties. 44,45,46 Indeed, since the emission origins from the Laporte forbiddent f-f transitions, lanthanide complexes display long lived excited state and narrow bandwidth emission band ranging from the visible to the near infra-red spectral range (NIR), with high emission efficiency and a large (pseudo)-Stokes shift that attracts considerable interests for molecular materials and imaging applications.…”

Highly efficient modulation of FRET in an orthogonally arranged BODIPY–DTE dyad

“…Promising candidates for the application as photoswitches are dithienylethenes (DTE) because of their reversible photoconversion between a colorless open and a colored closed form, their thermal stability and fatigue resistance 10 . Consequently, DTE has been assembled in molecular dyads or triads in combination with boron-dipyrromethene (BODIPY) 11 12 13 , anthracene 1 2 , oligothiophene 7 14 15 , perylene 16 , porphyrin 8 17 18 , rhodamine 19 , metal complexes 20 and semiconductor quantum dots 21 22 23 . In our recently published work we describe the photomodulation of electronic conjugation within BODIPY-diarylethene molecular dyads 13 .…”