Milan Shyamal

Pyrene Scaffold as Real-Time Fluorescent Turn-on Chemosensor for Selective Detection of Trace-Level Al(III) and Its Aggregation-Induced Emission Enhancement

A pyrene based fluorescent probe, 3-methoxy-2-((pyren-2yl-imino)methyl)phenol (HL), was synthesized via simple one-pot reaction from inexpensive reagents. It exhibited high sensitivity and selectivity toward Al(3+) over other relevant metal ions and also displayed novel aggregation-induced emission enhancement (AIEE) characteristics in its aggregate/solid state. When bound with Al(3+) in 1:1 mode, a significant fluorescence enhancement with a turn-on ratio of over ∼200-fold was triggered via chelation-enhanced fluorescence through sensor complex (Al-L) formation, and amusingly excess addition of Al(3+), dramatic enhancement of fluorescence intensity over manifold through aggregate formation was observed. The 1:1 stoichiometry of the sensor complex (Al-L) was calculated from Jobs plot based on UV-vis absorption titration. In addition, the binding site of sensor complex (Al-L) was well-established from the (1)H NMR titrations and also supported by the fluorescence reversibility by adding Al(3+) and EDTA sequentially. Intriguingly, the AIEE properties of HL may improve its impact and studied in CH3CN-H2O mixtures at high water content. To gain insight into the AIEE mechanism of the HL, the size and growth process of particles in different volume percentage of water and acetonitrile mixture were studied using time-resolved photoluminescence, dynamic light scattering, optical microscope, and scanning electron microscope. The molecules of HL are aggregated into ordered one-dimensional rod-shaped microcrystals that show obvious optical waveguide effect.

Crystal induced phosphorescence from Benz(a)anthracene microcrystals at room temperature.

Pure organic compounds that are also phosphorescent at room temperature are very rare in literature. Here, we report efficient phosphorescence emission from aggregated hydrosol of Benz(a)anthracene (BaA) at room temperature. Aggregated hydrosol of BaA has been synthesized by re-precipitation method and SDS is used as morphology directing agent. Morphology of the particles is characterized using optical and scanning electronic microcopy (SEM). Photophysical properties of the aggregated hydrosol are carried out using UV-vis, steady state and time resolved fluorescence study. The large stoke shifted structured emission from aggregated hydrosol of BaA has been explained due to phosphorescence emission of BaA at room temperature. In the crystalline state, the restricted intermolecular motions (RIM) such as rotations and vibrations are activated by crystal lattice. This rigidification effect makes the chromophore phosphorescent at room temperature. The possible stacking arrangement of the neighboring BaA within the aggregates has been substantiated by computing second order Fukui parameter as local reactivity descriptors. Computational study also reveals that the neighboring BaA molecules are present in parallel slipped conformation in its aggregated crystalline form.

Proton triggered emission and selective sensing of 2,4,6-trinitrophenol using a fluorescent hydrosol of 2-phenylquinoline

2-Phenylquinoline (PhQ) displayed novel aggregation induced emission enhancement (AIEE) characteristics in its aggregate/solid state. It also allows reversible fluorescence switching in acidic and basic media and changes the emission color from sky blue to intense blue in its aggregate state through protonation. Such behavior enables it to be utilized as a fluorescent pH sensor in acidic and basic media. PhQ microparticles with distinct morphologies are synthesized through a reprecipitation method and SDS is used as the morphology directing agent. The photophysical properties, size and growth process of the particles are characterized by UV-Vis absorption, steady state and time resolved spectroscopy, optical and scanning electron microscopy studies. The “turn off” luminescence property of the aggregated PhQ hydrosol in the presence of 2,4,6-trinitrophenol (TNP) is used for the selective detection of trace amounts of TNP in water and the super-amplified fluorescence quenching has been explained as due to ground state complexation between PhQ and TNP.