Structurally simple thienodipyrandione-containing reversible fluorescent switching piezo- and acido-chromic materials

Abstract

We report here the structure-property correlations of a series of anthracene/pyrene derivatives grafted on a rigid, planar, and well conjugated endo-cyclic alkenyl lactone (thienodipyrandione) that exhibited aggregation induced emission. Unlike typical vinylene based solid-state fluorescence materials, rigid thienodipyrandione moieties can bestow a higher order of conformational twist as well as enhanced intermolecular interactions by C-H/O interactions due to the presence of a carbonyl group that leads to enhanced thermal stability. Compounds TDAn and TDAnPh exhibit distinct piezofluorochromic properties in which emission colors can be switched by grinding and heating. Based on a variety of spectroscopic techniques including XRD, DSC, and NMR, the observed piezochromic emission is attributed to the result of phase transition from structural crystalline (order) to amorphous (disorder) state or vice versa. Most uniquely, one of the anthracene derivatives, TDAn, displayed specific acidofluorochromism whereas the other congener, TDAnPh, did not, even though they are structurally very similar. Crystal structure analysis revealed that a combination of various secondary interactions such as C-H/O, p-p and C-H/p interactions all play key roles in the supramolecular assemblies to display such distinctive features. The current study has disclosed a class of new stimuli-responsive materials with great potential in applications for micro-environmental sensing, optical switching and recording.

Cross-Linked Fluorescent Supramolecular Nanoparticles as Finite Tattoo Pigments with Controllable Intradermal Retention Times

“…Aggregation of π -conjugated systems often resulted in the decrease of UV–visible light absorption. 33,34 Therefore, the absorption cross section should increase when polymer aggregations were disassembled in FSNPs.…”

Non‐classical S‐Heteroacenes with o‐Quinoidal Conjugation and Open‐Shell Diradical Character

“…The syntheses of the longer AT‐ n and ADT‐ n derivatives are based on the corresponding quinones (Scheme ). Suzuki coupling reactions between 2,5‐dibromo‐3,4‐diethylcarboxylthiophene 3 and phenyl boronic acid afforded the diester 4 , which was converted into the dialdehyde 5 by reduction with LiAlH 4 followed by oxidation of the intermediate diol with pyridinium chlorochromate (PCC). The quinones 6 a , 6 b , and 7 were then obtained from the condensation reaction between 5 and 1,4‐dihydroxynaphthalene, 1,4‐dihydroxyanthracene, and 1,4‐cyclohexanedione, respectively.…”

“…o ‐Dibenzoyllbenzene 1 , naphthalene‐2,3‐dibis(phenylmethanone) 2 , and 2,5‐dibromo‐3,4‐diethylcarboxylthiophene 3 were prepared according to the reported procedures.…”

Mechanochromic Luminescence Characteristics of Pyridine‐Terminated Chromophores in the Solid State and in a Poly(vinyl alcohol) Matrix

“…1 H and 13 C NMR spectra were measured in CDCl 3 at room temperature with tetramethylsilane (TMS; d = 0.00) as an internal standard. Electrospray ionization (ESI) mass spectra and total C, H and N content of the final compounds were measured with a gas chromatograph mass spectrometer (GC/MS; Shimadzu, GCMS-QP5050 A) and an elemental analyzer (Yanaco, MT-5), respectively.…”

“…Recently, Sun and co-workers reported a novel MCL behavior for an anthracene derivative without an acid-responsive unit; however, the dyes exhibited an acid-induced color change due to a phase transition from a crystalline powder to an amorphous solid. [13] Changes in the PL properties by acidic coordination enables fine-tuning of the color with a change in the acid species. In addition, properties such as film preparation, self-assembly, and liquid-crystallinity have been successfully achieved by the introduction of an acidic polymer film with a suitable acidic functional unit as the host material.…”