Strategic Insertion of Heavy Atom to Tailor TADF OLED Material for the Development of Type I Photosensitizing Catalytic Red Emissive Assemblies.

The work presented in the manuscript describes a simple strategy for transforming thermally activated delayed fluorescent organic light-emitting diodes (TADF OLEDs) compound 10-(dibenzo[a,c]phenazin-11-yl)-10H-phenoxazine (DPZ-PXZ) into type I photosensitizer 10-(dibenzo[a,c]phenazin-11-yl)-10H-phenothiazine (DPZ-PHZ) by strategically introducing sulfur atom in the photosensitizing core. The synthesized compound DPZ-PHZ exhibits aggregation-induced enhancement (AIE) and through-space charge transfer (TSCT) characteristics and generates red emissive assemblies in mixed aqueous media. The original compound DPZ-PXZ exhibits well-separated HOMO and LUMO levels and is reported to have highly efficient reverse intersystem crossing (RISC). In comparison, the incorporation of sulfur atom in the phenothiazine donor regulates the electronic communication between donor and acceptor units and promotes the intersystem crossing (ISC) in DPZ-PHZ molecules. Interestingly, compound DPZ-PHZ exhibits rapid activation of aerial oxygen for instant generation of superoxide radical anion. Backed by excellent type I photosensitizing activity, DPZ-PHZ assemblies have high catalytic potential for the synthesis of benzimidazoles, benzothiazoles and quinazolines derivatives under mild reaction conditions. The work presented in the manuscript provides an insight into the combination of heavy atom approach and TSCT for achieving adequate electronic communication between donor and acceptor units, balanced RISC/ISC, and stabilized-charge separated state for the development of efficient type I photosensitizing assemblies.

Nanophotosensitizing through Space Charge Transfer Assemblies of Pentacenequinone Derivative for 'Metal-free' Photoamidation Reactions.

The present study demonstrates the influence of small portion (20 %) of organic co-solvent (DMSO/THF/ACN/MeOH) in mixed aqueous media (80 % water) in controlling the size, quantum yield and life time of the through space charge transfer assemblies (TSCT) of pentacenequinone derivative (TPy-PCQ-TPy). Among various solvent systems [H2 O : DMSO (8 : 2), H2 O : THF (8 : 2), H2 O : ACN (8 : 2) and H2 O : MeOH (8 : 2)] examined, highly emissive (Φf =12 %) and nano-sized assemblies having long life time (3.11 ns) were formed in H2 O : DMSO (8 : 2) solvent system. The solvent dependent differences in the size and excited state properties of TPy-PCQ-TPy assemblies are reflected in their photosensitizing behaviour in different solvent systems. Backed by excellent photosensitizing properties, TPy-PCQ-TPy assemblies smoothly catalyse the photoamidation reactions between unactivated/activated aldehydes and secondary amine under mild reaction conditions (visible light irradiation, aerial atmosphere, room temperature) in H2 O : DMSO (8 : 2) solvent mixture. The as prepared assemblies of TPy-PCQ-TPy also exhibit high potential to catalyse the oxidation of benzyl alcohols to aromatic aldehydes, thus, generating a possibility to use aromatic alcohols as the starting material in photoamidation reactions. The real time application of TSCT assemblies has also been demonstrated in gram scale transformation of aromatic aldehydes to aromatic amides and photooxidation of benzyl alcohol to aromatic aldehyde.

Cobalt-Centered Supramolecular Nanoensemble for Regulated Aerobic Oxidation of Alcohols and "One-Pot" Synthesis of Quinazolin-4(3H)-ones.

The supramolecular assemblies of the donor-acceptor (D-A) system Im-Tpy, having phenanthro[9,10-d]imidazole as the donor and terpyridyl group as the acceptor unit, have been developed, which serve as supramolecular host to stabilize Co(II) in its nanoform. The as-prepared supramolecular nanoensemble Im-Tpy@Co in DMSO:water (7:3) shows high thermal stability and photostability. Even in the case of solvent mismatch, i.e., on dilution with cosolvent THF/DMSO, insignificant changes were observed in the size/morphology of the nanoensemble. The as-prepared Im-Tpy@Co nanoensemble in low catalytic loading (0.1 mol % of Co) catalyzes the oxidation of a wide variety of alcohols to aromatic aldehydes/ketones using visible light radiations as the source of energy without the need of any additive at room temperature. In comparison to already reported systems, the Im-Tpy@Co nanoensemble exhibits high turnover numbers (TONs) and turnover frequencies (TOFs). The practical application of the catalytic system has also been demonstrated in the gram-scale synthesis of 4-chlorobenzaldehyde. The Im-Tpy@Co nanoensemble exhibits recyclability up to four catalytic cycles with insignificant leaching and morphological changes. The present study also demonstrates the catalytic activity of the Im-Tpy@Co nanoensemble in "one-pot" synthesis of quinazolin-4(3H)-ones from 2-aminobenzamide and primary alcohols with better efficiency in comparison to other transition-metal-based catalytic systems.

Beyond Molecular Recognition: A Perylene Bisimide Derivative as a Functional Mimic of Chlorpyrifos.

Supramolecular assemblies of perylene bisimide derivative (PBI-SAH) have been developed which show 'turn-on' detection of chlorpyrifos in aqueous media, apple residue and blood serum. Differently from the already reported fluorescent probes for the detection of CPF, PBI-SAH assemblies also show affinity for acetylcholinesterase (AChE) which endow the PBI-SAH molecules with mixed inhibitory potential to restrict the AChE catalysed hydrolysis of acetylthiocholine (ATCh) in MG-63 cell lines (in vitro) and in mice (in vivo). The molecular docking studies support the inhibitory activity of PBI-SAH assemblies and their potential to act as safe insecticide with high benefit to harm ratio. The insecticidal potential of PBI-SAH derivative has been examined against Spodoptera litura (S. litura) and these studies demonstrate its excellent insecticidal activity (100 % mortality in nineteen days). To the best of our knowledge, this is the first report regarding development of PBI-SAH assemblies which not only detect chlorpyrifos but also mimic AChE inhibitory activity of CPF to show promising aptitude as safe insecticide.

Aggregation-Induced Emission (AIE), Life and Health.

Light has profoundly impacted modern medicine and healthcare, with numerous luminescent agents and imaging techniques currently being used to assess health and treat diseases. As an emerging concept in luminescence, aggregation-induced emission (AIE) has shown great potential in biological applications due to its advantages in terms of brightness, biocompatibility, photostability, and positive correlation with concentration. This review provides a comprehensive summary of AIE luminogens applied in imaging of biological structure and dynamic physiological processes, disease diagnosis and treatment, and detection and monitoring of specific analytes, followed by representative works. Discussions on critical issues and perspectives on future directions are also included. This review aims to stimulate the interest of researchers from different fields, including chemistry, biology, materials science, medicine, etc., thus promoting the development of AIE in the fields of life and health.

Enzyme-/metal-free quinoxaline assemblies: direct light-up detection of cholesterol in human serum.

Supramolecular assemblies of quinoxaline derivative (QxPyA) have been developed for turn-on detection of cholesterol in human serum and in aqueous media with a detection limit of 4 nM.

Controlling the Transition of Nanospheres to Superhelices in Aqueous Media by Using a "Smart" Pyrazine Building Block.

For the development of nature-inspired chiral nanostructures, controlling the chirality communication along the assembling pathways in aqueous media is a crucial task. Herein, we designed and synthesized pyrazine-based derivative Pyra-Met with an L-methionine group as a chiral handle. Due to the presence of flexible side chains in the Pyra-Met building block, its interactions with the solvent molecules in the assembled state are restricted, which leads to the generation of nanospheres in aqueous media. The Pyra-Met nanospheres selectively interact with Au3+ ions to generate dynamic helical fibers of the Pyra-Met:Au3+ ensemble with 'hidden' chirality. Finally, superhelices with the desired helical sense are achieved in the presence of L/D-methionine via a co-assembly process. This work presents a feasible strategy to achieve the desired handedness of supramolecular assemblies for better understanding of chirality translation in supramolecular chemistry and it highlights the importance of fine tailoring of building block to control the morphology of the assembled architecture.

ESIPT Active Assemblies for 'On-On' Detection, Cell Imaging and Hampering Cellular Activity of 2,6-Dichloro-4-nitroaniline.

ESIPT active PBI-keto/enol assemblies have been developed which show 'on-on' optical response towards 2,6-dichloro-4-nitroaniline (DCN) due to a combined ESIPT-AIEE phenomenon with a detection limit of 1.65 nM. The potential of PBI-keto/enol assemblies to detect DCN has also been explored in grape juice/grape residue and soil for six consecutive days. Further, the biological applications of PBI-keto/enol assemblies to detect DCN in blood serum, in MG-63 cell lines and their ability to restrict the DCN-induced cell death have been demonstrated.

Type†I 'Lighted Metal-free' Photosensitizing Assemblies of Phenazine for Aerobic Oxidative Transformations.

Highly photostable supramolecular photosensitizing 'lighted metal-free' assemblies of DPZ-Th have been developed which show strong absorption in the visible region and excellent electron transportation potential from donor to acceptor units. The as-prepared assemblies of DPZ-Th activate aerial oxygen to generate Type I reactive oxygen species (ROS) under visible-light irradiation in mixed aqueous media. Owing to these properties, the as-prepared DPZ-Th assemblies exhibit high photocatalytic activity in catalyzing the aerobic oxidative coupling of benzylamines and synthesis of quinazolines. Various spectroscopic studies support the participation of Type I reactive species in the reaction mechanism. The 'pure' oxygen environment was not needed for carrying out these transformations and all the reactions proceed very well under aerial conditions to furnish the desired products in high yields.

AIE materials for lysosome imaging.

The aggregation-induced emission (AIE) active bioprobes are known for their high photostability and extraordinary signal to noise ratio. In view of this, research efforts to synthesize new AIE bioimaging probes are at an incredible speed. In this chapter, we have summarized the various lysosome specific AIE active "turn-on" bioprobes having applications in lysosome imaging, monitoring of lysosome bioactivity and evaluation of their therapeutic effects. By discussing their design and operational mechanisms, we hope to provide more insight into designing new AIE bioprobes for specific sensing and imaging of lysosome having flexibility for broad range of biomedical applications.

Fluorescent molecular probe-based activity and inhibition monitoring of histone deacetylases.

Extensive studies in recent decades have revealed that gene expression regulation is not limited to genetic mutations but also to processes that do not alter the genetic sequence. Post-translational histone modification is one of these processes in addition to DNA or RNA modifications. Histone modifications are essential in controlling histone functions and play a vital role in cellular gene expression. The reversible histone acetylation, regulated by histone acetyltransferases (HATs) and histone deacetylases (HDACs), is an example of such modifications. HDACs are involved in the deacetylation of histones and lead to the termination of gene expression. Although this cellular process is essential, upregulation of HDACs is found in numerous cancers. Therefore, research related to the activity and inhibition monitoring of HDACs is necessary to gain profound knowledge of these enzymes and evaluate the success of the therapeutic approach. In this perspective, methodology derived from fluorescent molecular probes is one of the preferable methods. Herein, we describe fluorescent probes developed to target HDACs by considering their activity and inhibition characteristics.

Pyrazine Based Type-I Sensitizing Assemblies for Photoreduction of Cu(II) in 'One-Pot Three-Component' CuAAC Reaction Under Aerial Conditions.

Photosensitizing assemblies of pyrazine derivative PDA have been developed which exhibit a high photostability, 'lighted' excited state, balanced redox potential, high transportation potential and activate oxygen via type-I pathway only. These PDA assemblies in combination with Cu(II) ions catalyze the CuAAC reaction via in situ reduction of Cu(II) ions without any reducing or stabilizing agent. The present protocol has wide substrate scope with recyclability of the catalytic system up to six catalytic cycles and is applicable to gram-scale synthesis.

'Light-Up' AIE-Active Materials: Self-Assembly, Molecular Recognition and Catalytic Applications.

Aggregation induced emission enhancement (AIEE) is one of the most widely explored phenomena to develop 'light up' (fluorescent) materials having potential applications in the field of supramolecular chemistry, analytical chemistry and material chemistry. By applying the principles of host-guest chemistry, we have developed a variety of aggregation induced emission (AIE/AEE) active materials having specific affinity for metal ions, electron deficient/electron rich analytes. The interactions between AIE active assemblies and metal ions are further tuned to prepare nanohybrids having potential applications as catalytic/photocatalytic systems in various organic transformations under eco-friendly conditions. This account summarizes various design strategies developed in our labortary for the preparation of AIE/AEE active building blocks having sensing and catalytic applications.

"Metal-Free" Nanoassemblies of AIEE-ICT-Active Pyrazine Derivative: Efficient Photoredox System for the Synthesis of Benzimidazoles.

Supramolecular nanoassemblies of an AIEE-ICT-active pyrazine derivative (TETPY) having strong absorption in the visible region and excellent transportability have been utilized as an efficient photoredox catalytic system for the synthesis of a variety of benzimidazoles having electron-withdrawing/electron-releasing/aliphatic groups under "metal-free" conditions. The reaction protocol involves the successful harvesting of visible light by TETPY assemblies to catalyze the coupling of o-phenylenediamine/substituted diamines and substituted aromatic/heterocyclic/aliphatic aldehydes under aerial conditions using mixed aqueous media as the reaction solvent. TETPY assemblies could activate aerial oxygen to generate superoxide for completing the vital proton abstraction step without the need for any external metal/base/oxidant. Moreover, all the products are purified by recrystallization from organic solvents. The TETPY assemblies also exhibited high efficiency in catalyzing the synthesis of 2-substituted benzothiazoles and quinazolines in excellent yields.

"Metal-Free" Fluorescent Supramolecular Assemblies for Distinct Detection of Organophosphate/Organochlorine Pesticides.

The "metal-free", easy-to-prepare fluorescent supramolecular assemblies based on anthracene/perylene bisamide (PBI) derivatives have been developed for the distinct detection of organophosphate (CPF) and organochlorine (DCN) pesticides in aqueous media. The supramolecular assemblies of anthracene derivative show rapid and highly selective "on-on" response toward organophosphate (CPF), which is attributed to the formation of CPF-induced formation of "closely packed" assemblies. A detection limit in the nanomolar range is observed for CPF. On the other hand, the inner filter effect is proposed as the mechanism for the "on-off" detection of DCN using supramolecular assemblies of the anthracene derivative. This is the first report on the development of fluorescent materials having the potential to differentiate between organophosphate and organochlorine pesticides. The assemblies of anthracene derivative 2 also act as "enzyme mimic" as organophosphate pesticide show a preferential affinity for assemblies of derivative 2 over acetylcholinesterase enzyme. Further, the real-time applications of supramolecular assemblies have also been explored for the detection of CPF and DCN in spiked water and in agricultural products such as grapes and apples.

Phenazine-Based Donor Acceptor Systems as Organic Photocatalysts for "Metal-free" C-N/C-C Cross-Coupling.

With an aim to achieve a balance between ground-state and excited-state reduction potential of donor acceptor systems for efficient C-N/C-C cross-coupling, a series of donor acceptor systems DA1-DA4 have been synthesized by varying the donor strength and connecting positions. With an increase in donor strength, systematic elevation in the ground-state reduction potential and decrease in the HOMO-LUMO gap was observed. Interestingly, all the derivatives DA1-DA4 could catalyze the C-N bond formation reaction between activated aryl halides and amines at low catalytic loading under metal-free conditions without the need of any external base upon irradiation with white LED. A balance was realized in the case of derivative DA2, which exhibits high efficiency in C-N couplings. Different control experiments support the validity of the energy as well as electron transfer pathways in the visible light-mediated C-N bond formation. This study further reveals the potential of derivative DA1 in "metal-free" Sonogashira coupling involving activated aryl halides which is attributed to its high excited-state reduction potential.

Integrating CuO-Fe2 O3 Nanocomposites and Supramolecular Assemblies of Phenazine for Visible-Light Photoredox Catalysis.

A photoredox catalytic ensemble consisting of CuO-Fe2 O3 nanocomposites and oligomeric derivative of phenazine has been developed. The prepared system acts as an efficient photoredox catalyst for C-N bond formation reaction via SET mechanism under 'green' conditions (aerial environment, mixed aqueous media, recyclable), requiring less equivalents of base and amine substrate. The present study demonstrates the significant role of supramolecular assemblies as photooxidants and reductants upon irradiation and their important contribution towards the activation of the metallic centre through energy transfer and electron transfer pathways. The potential of oligomer 4: CuO-Fe2 O3 has also been explored for C-C bond formation reactions via the Sonogashira protocol.

Design and Applications of Small Molecular Probes for Calcium Detection.

The physiological significance of calcium ions such as the role in cellular signalling, cell growth, etc. have driven the development of methods to detect and monitor the level of Ca2+ ions, both in vivo and in vitro. Although various approaches for the detection of calcium ions have been reported, methods based on small molecular fluorescent probes have unique advantages including small probe size, easy monitoring of detection processes and applicability in biological systems. In this review article, we will discuss the progress in the development of Ca2+ -binding fluorescent probes by taking into account the types of chelating groups that have been employed for Ca2+ binding.

Entropically Favoured Assembly of Pyrazine-Based Helical Fibers into Superstructures: Achiral/ Chiral Guest-Induced Chirality Transformation.

The development of synthetic helical structures undergoing stimuli-responsive chirality transformations is important for an understanding of the role of chirality in natural systems. However, controlling supramolecular chirality in entropically driven assemblies in aqueous media is challenging. To develop stimuli-responsive assemblies, we designed and synthesized pyrazine derivatives with l-alanine groups as chiral building blocks. These systems undergo self-assembly in aqueous media to generate helical fibers and the embedded alanine groups transfer their chirality to the assembled structures. Furthermore, these helical fibers undergo a Ni2+ -induced chirality transformation. The study demonstrates the role of intermolecular hydrogen bonding, π-π stacking, and the hydrophobic effect in the Ni2+ -mediated transition of helical fibers to supercoiled helical ensembles which mimic the formation of superstructures in biopolymers.

AIEE Active Nanoassemblies of Pyrazine Based Organic Photosensitizers as Efficient Metal-Free Supramolecular Photoredox Catalytic Systems.

Pyrazine derivatives DIPY, TETPY and CNDIPY have been designed and synthesized which form fluorescent supramolecular assemblies in mixed aqueous media due to their AIEE and ICT characteristics. Among all the derivatives, the assemblies of TETPY and CNDIPY show strong absorption in the visible region with high absorption coefficients, low HOMO-LUMO gap, and high photostability. Further, the supramolecular nanoassemblies of TETPY and CNDIPY show excellent potential to generate reactive oxygen species (ROS) under the visible light irradiation. Owing to their strong absorption in the visible region and ROS generation ability, the supramolecular nanoassemblies of TETPY and CNDIPY act as efficient photoredox catalytic systems for carrying out (a) oxidative amidation of aromatic aldehydes (b) hydroxylation of boronic acid and (c) oxidative homocoupling of benzylamines under mild conditions such as aqueous media, aerial environment, and natural sunlight as a source of irradiation. All the mechanistic investigations suggest the participation of in-situ generated ROS in the organic transformations upon light irradiation.