Fluorescence modulation of naphthalene containing salicyl hydrazide-based receptor through aggregation-induced emission enhancement approach: Dual detection of lanthanum and cyanide ions in semi-aqueous medium.

The sensing activity of naphthalene containing salicyl hydrazide-based fluorescence receptor has been improved through aggregation-induced enhanced emission mechanism approach in semi-aqueous medium. The receptor has been found to be selective toward La3+ with approximately 70-fold fluorescence enhancement due to a combined effect of keto-enol tautomerism inhibition and chelation enhanced fluorescence with a detection limit of 3.91 × 10-6 M. In addition, the receptor is also able to sense CN- with a detection limit of 3.55 × 10-6 M via deprotonation effect, justifying its multiple analyte sensing behaviour. Hence, the current analytical methodology improves the sensing activity of the probe and also provides a greener alternative for La3+ and CN- detection.

Exploration of solvent responsive Cr3+-Schiff base conjugates formonitoring Cr3+ ions and organophosphates: Fabrication of spot-testingdevices.

Herein, we report 2-((2-hydroxybenzylidene)hydrazono)(phenyl)methyl)-5-methoxyphenol (SB) synthesized by Schiff base condensation and characterized by spectroscopic techniques, elemental analysis and X-ray crystallography. In solution phase, it interacts with Cr3+ ions and exhibits a prominent fluorimetric switch due to the formation of SB·Cr3+ conjugate. The dual behavior of SB·Cr3+ conjugates i.e. self-aggregation in high water fraction (fw > 50%) and dissolution in low water fraction (fw < 50%) proves this conjugation excellent tool for monitoring Cr3+ ions. The SB·Cr3+ conjugate in methanol-water (70:30 v/v) allows quantification of Cr3+ ions with limit of detection 0.44 µM and its self-aggregation in high water fraction facilitates extraction of Cr3+ ions with 95% extraction efficiency. Although SB interacts with Zn2+ ions which causes inference in the determination of Cr3+ ions however the interferent can be easily masked with SCN- ions. Besides, the SB·Cr3+ conjugates are also able to quantify organophosphate neurotoxins; i.e. diethyl chlorophosphate (with LOD 4.1 nM) and diethyl cyanophosphonate (with LOD 3.3 nM) from aqueous solutions. Moreover, SB and SB·Cr3+ conjugates can be coated on solid surfaces to fabricate portable devices for the on-spot detection of targets from real samples. Hence, the conjugation of Schiff base and Cr3+ ions can be explored for the recognition, quantification and extraction of Cr3+ ions and detection of organophosphates.

Catalyst-Controlled Structural Divergence: Selective Intramolecular 7-endo-dig and 6-exo-dig Post-Ugi Cyclization for the Synthesis of Benzoxazepinones and Benzoxazinones.

Metal catalyzed post-Ugi cyclization of bis-amides is reported in this study. Exposure of bis-amides to Pd(II) catalyst triggered the formation of seven-membered benzoxazepinones. This investigation established that changing the catalyst to a Echavarren's gold(I) turned off cyclization to seven member ring and turned on 6-exo-dig annulations to afford family of six-membered benzoxazinones. To support the proposed mechanisms, quantum chemical based density functional theory calculations have been performed and validated. This novel method obtained molecular complexity up to four modular inputs and divergence of two different skeletons. 2D NMR spectroscopic techniques and single crystal X-ray diffraction established the proposed structures.

The influence of different coordination environments on one-dimensional Cu(ii) coordination polymers for the photo-degradation of organic dyes.

Three new Cu(ii) coordination polymers, namely, {[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n (), [Cu3(L(1))(Cl)2(DMF)2]n () and [Cu3(L(2))(NO3)4(H2O)4]n (), were synthesized from pyridine-2,6-dicarbohydrazide based imine linked tritopic ligands. All the complexes were characterized using elemental analysis, IR, UV-vis spectroscopy and ESI-MS. The solid state structures of complexes were determined using single crystal X-ray crystallography. The complexes contain trinuclear copper units connected through different anions that lead to the formation of one dimensional (ID) chain structures. Depending upon the anion of the copper salt and donor atoms of the ligands used in complexation, a small variation in the structures was observed. In complex , the trinuclear copper units are connected by phenoxo-bridging (µ2-O(-)) along with one coordinated water molecule, whereas complex is connected through chloride bridging (µ2-Cl) and complex is connected through nitrate ions (µ-[O-N-O]) along with four water molecules. Photo-catalytic activities of the synthesized complexes () were investigated. All the complexes were found to be photo-catalytically active; however, the distinct coordination environment of the metal ions (i.e. difference in the coordinated water molecules and donor sites of ligands) played a significant role in the catalytic activities. Therefore, this study presents comparative photo-catalytic studies of different coordination environments of metal ions in one-dimensional Cu(ii) coordination polymers. The results provide a potential pathway for the rational design of more efficient photo-catalysts.

Potassium induced stitching of a flexible tripodal ligand into a bi-metallic two-dimensional coordination polymer for photo-degradation of organic dyes.

A novel strategy for the stitching of a tripodal ligand into a bi-metallic two-dimensional (2D) coordination polymer has been reported. The reaction of 5-nitrosalicylaldehyde based ligand H3L with nickel acetate resulted in the metal functionalized 2D extended network via potassium induced activation of the nitro group of the ligand. The compound is highly active towards photo-degradation of organic dyes.

Comparative DNA binding abilities and phosphatase-like activities of mono-, di-, and trinuclear Ni(II) complexes: the influence of ligand denticity, metal-metal distance, and coordinating solvent/anion on kinetics studies.

Six novel Ni(II) complexes, namely, [Ni2(HL(1))(OAc)2] (1), [Ni3L(1)2]·H2O·2CH3CN (2), [Ni2(L(2))(L(3))(CH3CN)] (3), [Ni2(L(2))2(H2O)2] (4), [Ni2(L(2))2(DMF)2]2·2H2O (5), and [Ni(HL(2))2]·H2O (6), were synthesized by reacting nitrophenol-based tripodal (H3L(1)) and dipodal (H2L(2)) Schiff base ligands with Ni(II) metal salts at ambient conditions. All the complexes were fully characterized with different spectroscopic techniques such as elemental analyses, IR, UV-vis spectroscopy, and electrospray ionization mass spectrometry. The solid-state structures of 2, 3, 5, and 6 were determined using single-crystal X-ray crystallography. The compounds 1, 3, 4, and 5 are dinuclear complexes where the two Ni(II) centers have octahedral geometry with bridging phenoxo groups. Compound 2 is a trinuclear complex with two different types of Ni(II) centers. In compound 3 one of the Ni(II) centers has a coordinated acetonitrile molecule, whereas in compound 4, a water molecule has occupied one coordination site of each Ni(II) center. In complex 5, the coordinated water of complex 4 was displaced by the dimethylformamide (DMF) during its crystallization. Complex 6 is mononuclear with two amine-bis(phenolate) ligands in scissorlike fashion around the Ni(II) metal center. The single crystals of 1 and 4 could not be obtained; however, from the spectroscopic data and physicochemical properties (electronic and redox properties) it was assumed that the structures of these complexes are quite similar to other analogues. DNA binding abilities and phosphatase-like activities of all characterized complexes were also investigated. The ligand denticity, coordinated anions/solvents (such as acetate, acetonitrile, water, and DMF), and cooperative action of two metal centers play a significant role in the phosphate ester bond cleavage of 2-hydroxypropyl-p-nitropenylphosphate by transesterification mechanism. Complex 3 exhibits highest activity among complexes 1-6 with 3.86 × 10(5) times greater rate enhancement than uncatalyzed reaction.

Ratiometric fluorescent probe for biothiol in aqueous medium with fluorescent organic nanoparticles.

A dipodal rhodamine-based mercury complex have been designed and synthesized, for the selective detection of 3-mercaptopropionic acid (MPA). To avoid the poor solubility of rhodamine-based ligand in pure water, the Hg(2+) complex of fluorescent organic nanoparticles (FONs) of ligand have been developed using reprecipitation method and the formation of 1:1 complex has been confirmed with various spectroscopic techniques. The resultant chemosensor can detect MPA in a concentration range of 60 nM-1 µM (in buffered aqueous medium) with detection limit of 60 nM.

Highly selective turn-on fluorescent sensor for nanomolar detection of biologically important Zn2+ based on isonicotinohydrazide derivative: application in cellular imaging.

A new Zn(2+) selective chemosensor (3) was synthesized by condensation of commercially available substituted salicylaldehyde and isonicotinohydrazide, and characterized by single crystal X-ray crystallography. Receptor 3 with Zn(2+) exhibited a highly selective and pronounced enhancement in the fluorescence emission among different cations by forming a 2:1 complex. The receptor can detect Zn(2+) up to nanomolar level (6.75 nM) with good tolerance of other metal ions and can be used for in vitro cellular imaging.