Concentration-Guided Visual Detection of Multiphase Aliphatic Biogenic Amines through Amine-Phenol Recognition Using a Dual-State Emitter.

Intermolecular amine-phenol interactions are largely recognized as unique models with diverse supramolecular interactions. However, fluorescence (FL) variations originating from such interactions are rare. Herein, FL changes are well realized from amine-phenol interactions to identify an important biomarker, biogenic amines (BAs). A simple, inexpensive, and thermally stable anthracenylphosphonate is linked with 2,2'-biphenol to design a functional dual-state emitter. Among the various amines tested, this emitter displays superior sensitivity with the lowest possible limit of detection as 5.8-9.7 ppb with aliphatic polyamines such as 1,3-, 1,4-, 1,5-, and 1,6- diamines and spermidine in the solution phase. Fast, on-spot detection of the BA vapors was visually conducted through a notable high-contrast change from blue to yellow emission in the solid state. FT-IR, 1H/31P NMR, and mass spectroscopic studies identify the ground-state amine-phenol interactions. The failure in BA detection with the 2,2'-dimethoxy-biphenyl-linked analog verifies the role of amine-phenol interactions. Mechanistic studies determine amine-phenol interactions in the ground and excited states. The molecular structure and packing of the doubly twisted probe are documented with a substantial void space facilitating close contact of the BAs with the strong amine-phenol interactions desired for efficient detection. Finally, this probe governs the freshness of a piece of Catla catla fish and prawn. Further, a remarkable concentration-controlled diverse emission with a red shift difference of 141 nm is detected with 1,3-diaminopropane (1,3-DAP) vapor (from 29 to 319 mg/L) for the first time. Thus, a cost-effective device is developed to detect 1,3-DAP at a precise concentration, visible through the naked eye.

A C3-symmetric twisted organic salt as an efficient mechano-/thermo-responsive molecule: a reusable and sensitive fluorescent thermometer.

C 3-Symmetric triaminoguanidinium chloride is condensed with N-pentylphenothiazine carboxaldehyde to realise a thermally stable twisted organic salt on a gram scale. It appears as a nonmetallic economic salt having an integrated propeller shape with three tub-like cores and displays efficient reversible mechano- and thermo-fluorochromic behaviour. Unlike previous reports, the designed fluorescent, colorimetric thermometer works over a higher temperature range of 130-170 °C with five distinct colour variations.

Mechanofluorochromic Anthryl Phosphonate/Benzoic Acid Cocrystals with a Large Blue Shift: The Role of P=O⋠⋠⋠H Interactions.

Organophosphonates have a rich and diverse chemistry, but their mechanofluorochromic features have rarely been documented. Herein, we report on cocrystals of anthranylphosphonate with (E)-4-(2-(anthracen-9-yl)vinyl)benzoic acid that exhibit reversible mechanofluorochromic properties with large blue shifts. Anisotropic grinding (or pressure of just 25 kPa) maintains the co-crystals emission features but leads to a pronounced 59 nm (2087 cm-1 ) blue-shift. Such an impressive blue-shift for a cocrystal has not been reported to date. The underlying causes for the blue-shift were validated by X-ray diffraction (powder and single crystal) studies and Hirshfeld surface analysis. Twisted molecular conformations and P=O⋅⋅⋅ H/C=O⋅⋅⋅H/C⋅⋅⋅H noncovalent interactions afford molecular arrangements via slip-stacks with two different pitch angles and relatively larger interlayer distances. The new compound was established as a potential medium for optical recording and security display.

An electron-rich small AIEgen as a solid platform for the selective and ultrasensitive on-site visual detection of TNT in the solid, solution and vapor states.

Promising research on AIEgen (aggregation-induced emission active fluorogens)-based sensors for the detection of explosives (mostly picric acid) is primarily dominated by polymeric molecules. However, herein, we report the ability of a recently developed anthracene-based electron-rich π-conjugate as a small and suitable AIEgen for the selective and sensitive detection of 2,4,6-trinitrotoluene (TNT) through fluorescence (PL) quenching. This fluorophore consists of trimethoxybenzene-linked anthranyl-π-phenothiazine, which is recognized as a significantly electron-rich AIEgen suitable for the selective detection of TNT detection. The detection of TNT was performed in the solid, liquid and vapor states using this AIEgen in the aggregate or solid-state. The detection limit in the solution state was measured to be 3.2 × 10-9 M. When this fluorophore was impregnated on a paper strip for on-site visual detection, TNT was detected up to the 10-14 M level by the naked eye using a 365 nm UV-torch. The paper strip was also successfully used to detect TNT in the vapour state. This application was further extended to detect TNT in field soil. The detection of TNT by replacing trimethoxybenzene in the fluorophore with dimethoxy or monomethoxy was a failure, indicating the requirement of an adequate electron-rich system. Unlike the previous report with static quenching as the main reason for TNT detection, our experimental observations demonstrated the participation of favorable photo-induced electron transfer (PET) between TNT and the fluorophore as the origin of the PL quenching.

Carbazole-Anthranyl π-Conjugates as Small and Stable Aggregation-Induced Emission-Active Fluorogens: Serving as a Reusable and Efficient Platform for Anticounterfeiting Applications with an Acid Key and Multicolor Ink for a Quill Pen.

Being a unique, simple, and inexpensive approach, continuous development on the fluorescence-based technologies remains active in fluorescent anticounterfeiting. A number of polymeric, nano-, carbon dot, and rare-earth oxide materials were preferably explored for such applications, but the complex synthesis, purity, and high cost are the major concerns to make these materials accessible for commercial applications. To address these difficulties, we herein report simple mono-carbazole-linked anthranyl π-conjugates that are synthesized in a gram scale via an inexpensive and convenient route. These unsymmetrically substituted new π-conjugates are found to be promising blue-shifted aggregation-induced emission-active fluorogens (AIEgens) having a distinct color on varying substituents with electron-rich (-NEt2) and electron-poor (-CN) functionalities. The direct link of a single carbazole unit with an anthracenyl π-conjugate possibly enforces the achievement of a highly twisted molecular structure, accountable for the AIE characteristics. The π-conjugate with -NEt2 substituents is established to be highly sensitive under protonation-deprotonation stimuli by a sharp and rapid fluorescence color change [yellow (Φf = 37%) to green (Φf = 39.4%)] in the solid state (no fluorescence on/off). Upon the exposure of the base vapors (deprotonation), the original emission color (yellow) comes back. Such reversible and also repeatable acidchromism is demonstrated to be perfectly suitable for anticounterfeiting applications by marking the AIEgen on the paper that shows the bright image of the AIEgen under the UV torch (365 nm). Almost equal efficiencies by fabricating on different surfaces such as polythene paper and a fresh leaf are observed. While these spots can be duplicated with typical yellow fluorescent dyes, our AIEgen can easily be differentiated with the acid key. The emission color change of this AIEgen from yellow to green under acid stimuli is distinctly defined compared to other dyes and vividly recognized by naked eyes. Thus, one can combat the counterfeiters with the acid key. The reversible color-changing behavior on the paper remains intact even after six consecutive days of exposure to sunlight, and the AIEgen is thermally stable up to 445 °C. Further, this compound is also utilized as ink (10 µM 1,4-dioxane solution) where a pigeon feather is used as a quill pen. The mechanistic insights behind these facts have also been proposed and validated wherever possible.

Positional Variation of Monopyridyl-N in Unsymmetrical Anthracenyl π-Conjugates: Difference between Solution- and Aggregate-State Emission Behavior.

Fluorescence enhancement on aggregation for π-conjugates linked with pyridyl ring has been established as a part of widely studied smart organic functional materials. Therefore, the photophysical features in the solution and aggregate states for such compounds remain impressive. In this work, we synthesized three series of photostable unsymmetrical aryl-substituted anthracenyl π-conjugates linked to pyridyl ring with a variation of the position of a pyridyl-N atom and examined the difference in the photophysical properties preferably in the aggregate state. The so-called "aggregation-induced emission (AIE)" behavior was discernible for the 2- and 4-pyridyl- but not 3-pyridyl-10-p-tolyl or mesityl-substituted π-conjugates. Curiously, a variation of the position of a pyridyl-N atom does not solely control the AIE phenomenon for 10-thiophenyl-substituted π-conjugates, where all of the isomers are found to be AIE-active. Hence, the dissimilarity in emission behavior in the aggregate state is governed by the position of N-atom for pyridine and also the substituent at the 10th position of the anthracyl ring. The mechanistic insight behind these observations is demonstrated by concentration-dependent fluorescence studies, time-resolved fluorescence, single-crystal X-ray diffraction studies (largely supportive to understand the molecular structure and packing in the aggregate), and average particle size measurement of the aggregates and partly by the density functional theory studies for a few representative molecules.

Weak Donor-/Strong Acceptor-Linked Anthracenyl π-Conjugates as Solvato(fluoro)chromophore and AEEgens: Contrast between Nitro and Cyano Functionality.

Steady development on photophysical behaviors for a variety of organic fluorophores inspired us to generate anthracene-based fluorescent molecules with a strong acceptor and a significantly weak donor through a π-spacer. Such molecules are found to have substantial twisted conformational orientations in the solid state and enhanced apolar character because of the attachment of tolyl or mesityl group with an anthracenyl core. Upon exposure to a variety of solvents, strong solvatochromism was noticed for 4-nitro compound (84 nm red shift) in contrast to the cyano analogue (18 nm red shift). Both these probes were highly emissive in apolar solvents while nitro-analogue, in particular, could discriminate the solvents of E T(30) (a measure of microscopic solvent polarity) ranging from 31 to 37. Thus, 4-nitro compounds can be successfully employed to detect and differentiate the apolar solvents. On the contrary, the 2-nitro analogue is almost nonemissive for the same range of solvents perhaps because of favorable excited-state intramolecular proton-transfer process. The fundamental understanding of solvatochromic properties through the formation of twisted intramolecular charge-transfer (TICT) state is experimentally analyzed by synthesizing and studying the π-conjugates linked to only benzene in place of nitro or cyanobenzene, which exhibits no solvatochromism and that helped finding the possible emission, originated from the locally excited state. Moreover, the molecular structures for these compounds are determined by the single-crystal X-ray diffraction studies to examine the change in emission properties with molecular packing and alignment in the aggregated state. The measurement of dihedral angles between the substituents and anthracenyl core was helpful in finding the possible extent of electronic conjugations within the system to decipher both solvatochromism and aggregation enhanced emission (AEE)-behavior. The cyano analogue exhibited prominent AEE-behavior, whereas nitro analogues showed the aggregation-caused quenching effect. The reason behind such dissimilarity in solvatochromism and AEE-behavior between cyano- and nitro-linked anthracenyl π-conjugates are also addressed through experimental outcomes.