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Terpyridine (TP) integrated with tetraphenylethylene (TPE-TP), pyrene (Py-TP) and triphenylamine (TPA-TP) exhibited structure controlled molecular packing and distinct fluorescence in the solid state. TPE-TP exhibited infinite aromatic π⋯π stacking between terpyridine units, Py-TP produced an isolated pyrene dimer, and TPA-TP displayed helical assembly via weak intermolecular H-bonding in the crystal lattice. The different molecular assembly of TPE-TP, TPA-TP and Py-TP produced a locally excited (LE) state, charge transfer (CT) state and excimeric emission at 460, 520 and 568 nm, respectively, in the solid state. Interestingly, the different molecular packing of TPE-TP, Py-TP and TPA-TP produced varied mechanofluorochromism. TPA-TP exhibited on–off reversible fluorescence switching upon mechanical crushing and heating, whereas TPE-TP and Py-TP displayed switching between two fluorescence states but in opposite directions. Crushing caused red shift of emission in TPE-TP and blue shift in Py-TP. Both TPA-TP and Py-TP showed strong fluorescence in solution and crystalline states, but TPE-TP showed typical aggregation induced emission (AIE). Further, Py-TP and TPE-TP showed selective fluorescence sensing of picric acid in solution and solid matrix, respectively. TPA-TP exhibited sensing of nitroaromatics both in solution as well as in the solid state. Solid state fluorescence of TPA-TP and TPE-TP was further utilized for fabricating PVA polymer composite thin films and demonstrated reusable fluorescence sensing of nitroaromatics in aqueous medium. The PVA–fluorophore composite film exhibited clear fluorescence quenching upon immersing the thin film into 10−7 M picric acid. Thus, the present study demonstrates the role of molecular structure in developing stimuli-responsive fluorescence materials and reusable sensors. [ABSTRACT FROM AUTHOR]

Molecular structural tailoring is one of the versatile approaches for developing functional organic fluorescent molecules with desired properties for practical applications. In this manuscript, we report the synthesis of triphenylamine based boron complexes (TPA-BF2) with unusual thermofluorochromism and alkyl chain length controlled molecular fluorescent liquids/solids. TPA-BF2 complexes with ethyl, propyl, butyl and pentyl groups produced fluorescent solids whereas with hexyl, heptyl and octyl groups yielded fluorescent liquids. The longer-alkyl chain compounds significantly improved the fluorescence efficiency (quantum yield (Φf = 12.6%)) by inhibiting close arrangement of fluorophores. TPA-BF2-2 and TPA-BF2-3 showed very weak fluorescence (Φf = 1.9%). On the other hand, all complexes exhibited strong solvent polarity dependent tunable fluorescence in the solution state. Importantly, the ability to form multiple excited states (locally excited (LE), charge transfer (CT) and twisted intramolecular charge transfer (TICT) states) resulted in unusual fluorescence tuning and reversible thermofluorochromism. The conversion of CT emission at RT to LE state emission at 77 K (under liquid nitrogen) of TPA-BF2 complexes in CHCl3/toluene resulted in strong blue shifting, while warming towards RT, the TPA-BF2 CHCl3 solution showed unusual fluorescence tuning. The fluorescence λmax of TPA-BF2-2 was red shifted from 476 to 600 nm and then blue shifted to RT fluorescence (550 nm). Interestingly, TPA-BF2 complexes in solution and in the PMMA matrix showed clear phosphorescence at 77 K. The unusual fluorescence tuning while warming from 77 K is attributed to the phosphorescence emission coupled with fluorescence at room temperature. Notably, the fluorescence intensity at RT was relatively stronger compared to red shifted fluorescence intensity while warming. TPA-BF2 complexes in toluene showed strong linear enhancement of fluorescence intensity (1.9 to 2.5 times) with a blue shifted peak position upon increasing the temperature from 0 to 100 °C. The alkyl chain length exhibited a strong influence on the rate and extent of fluorescence tuning with temperature. Thus, alkyl group variations in simple Schiff base–boron complexes produced unusual thermofluorochromism and molecular fluorescent liquids. [ABSTRACT FROM AUTHOR]

pH-responsive fluorescence molecules are interesting candidates for achieving tunable as well as white light emission from a single molecule. Herein, we have synthesized pyridine-integrated carbazole and triphenylamine donor–acceptor isomers, (Z)-3-(4-(9H-carbazol-9-yl)phenyl)-2-(pyridinyl)acrylonitrile (1–3) and (Z)-3-(4-(diphenylamino)phenyl)-2-(pyridinyl)acrylonitrile (4–6), and studied the effects of the structure and solvent on acid-responsive fluorescence modulation in the solution state. Both carbazole (1–3) and triphenylamine (4–6) isomers produced twisted intramolecular charge transfer (TICT) states and showed tunable fluorescence depending on the solvent polarity. Highly blue shifted fluorescence was observed in non-polar toluene, while polar DMF showed large red-shifted fluorescence. Further, 1–3 isomers exhibited relatively strong fluorescence compared to 4–6. Interestingly, 1–6 exhibited organic acid-dependent (trifluoroacetic acid (TFA) and p-toluene sulphonic acid (PTSA)) and solvent-dependent fluorescence tuning. Carbazole isomers (1–3) showed wide fluorescence colour tuning from blue to red as well as white light emission in toluene, whereas green to red transition was observed in CHCl3. Addition of TFA, a stronger acid, to 1 and 3 afforded blue, green and red emission along with white emission in toluene, whereas weak PTSA produced blue and red emission along with white emission. In contrast, addition of TFA or PTSA to the triphenylamine isomers (4–6) exhibited complete quenching of fluorescence in all solvents. The meta-isomers did not show significant fluorescence tuning with acids. The wide fluorescence tuning of 1 in toluene with TFA has also been successfully transformed into a PMMA polymer matrix, which also exhibited clear fluorescence tuning from blue to red. Density functional theoretical (DFT) studies indicated high molecular twisting in the excited state and clear separation of charge transfer from the donor carbazole to the acceptor unit compared to the propeller-shaped triphenylamine isomer; this may contribute to the wide fluorescence tuning in the carbazole isomers. The present studies could be useful for choosing appropriate molecular structures and solvent systems for achieving wide fluorescence tuning and white light emission from a single donor–acceptor molecule. [ABSTRACT FROM AUTHOR]

Methoxy substitution at acceptor end of TPA-acetophenone fluorophore showed white light emission, tunable emission by morphological transformation and mechano-responsive reversible fluorescence switching. [Display omitted] • White light emission from single fluorophore by methoxy substitution. • Tunable fluorescence by methoxy substitution and morphological transformation. • Fluorescent polymorphs with tunable emission. • Stimuli-responsive reversible and self-reversible fluorescence switching. Introducing methoxy substituent into triphenylamine-acetophenone based donor-π-acceptor fluorophore, 3-(4-(diphenylamino)phenyl)-1-phenylprop-2-en-1-one (1), produced strong solvatofluorochromism including white light emission, fluorescent polymorphs and mechano-responsive fluorescence switching. The unsubstituted and methoxy substituted compounds displayed strong solvent polarity mediated tunable emission in the solution. Interestingly, 3-(4-(diphenylamino)phenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (2) and 3-(4-(diphenylamino)-2-methoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (3) showed single molecule white light emission in DMSO and ethanol, respectively. 1-3 exhibited strong green/yellow fluorescence in the solid-state (Quantum yield (Φ f) = 10 to 23%). 2 produced fluorescent polymorphs (green (2-G) and yellow (2-Y). Single crystal structural analysis revealed that donor and acceptor phenyl units adopted coplanar conformation in 2-G and 3 whereas twisted molecular conformation in 1 and 2-Y. Further, 2-G exhibited π...π interactions facilitated isolated dimers whereas 2-Y showed well separated molecules in the crystal lattice. Aggregation induced emission (AIE) studies showed morphological transformation induced fluorescence tuning for 2. The intramolecular charge transfer (ICT) from TPA to acetophenone was confirmed by computational studies. Mechanofluorochromic (MFC) studies of 1 showed only slight reduction of intensity without modulating fluorescence wavelength significantly but 2 and 3 exhibited visible emissive colour change from yellow to green and vice versa by crushing and heating. Both 2 and 3 also exhibited self-reversible fluorescence switching that was confirmed by PXRD pattern. Thus, methoxy group introduction resulted in obtaining white light emitting fluorescence molecules in the solution state and self-reversible fluorescence switching materials. [ABSTRACT FROM AUTHOR]

Triphenylamine (TPA) based di-aldehyde fluorophores have been synthesised and utilized for fabricating solid thin film fluorescence assay for hydrazine sensing and rewritable fluorescence platform. Addition of hydrazine reacts with aldehyde and strongly quenched the fluorescence intensity in solutions. Interestingly, fluorophores integrated into PMMA thin films showed strong blue fluorescence and exhibited turn-off fluorescence upon immersing in hydrazine solution (5%) and turn-on fluorescence by immersing in acetic acid (5%). Concentration dependent studies revealed the limit of detection (LOD) of 9.3–14.0 μM in solution and 0.021% by solid matrix. Reversible off-on fluorescence switching both in solution and PMMA matrix has been achieved by acid and base exposure that has been successfully used for demonstrating rewritable fluorescent platforms. Reusable solid fluorescent sensor and rewritable fluorescent platforms have been developed by integrating di-triphenylamine aldehyde fluorophore with PMMA matrix. Image 1 • Halochromic off-on fluorescence switching in solution as well as solid state. • Fabrication of rewritable fluorescence platforms. • Selective fluorescence sensing hydrazine. • PMMA based reusable solid fluorescence assay for hydrazine. [ABSTRACT FROM AUTHOR]