pH-responsive supramolecular switch of a rationally designed dipyrroethene-based chromophore.

Herein, we present a strategy to access a novel class of pH-responsive, dual-state emissive (DSE), highly fluorescent pyrrole-based chromophores diformylation of dipyrroethenes (DPE) followed by condensation with various aniline derivatives. The DPE-based chromophores exhibit a large Stokes shift and maintain good fluorescence quantum yields. Remarkably, these chromophores demonstrate reversible colourimetric changes and a fluorometric 'on-off-on' switch in response to pH variations.

Synthesis, structure, and spectral and electrochemical properties of new visible to NIR absorbing 3-pyrrolyl BODIPY derivatives.

We report the synthesis, characterization, and studies of novel 3-pyrrolyl BODIPY-based Schiff base products 3-6 and 3-pyrrolyl BODIPY-based benzo[]thiazol-2-yl derivatives 7-8. The Schiff base compounds 3-6 were synthesized condensation of α-formyl 3-pyrrolyl BODIPY with various amine derivatives, while the Knoevenagel condensation products 7-8 were obtained by reacting α-formyl 3-pyrrolyl BODIPY with 2-(benzo[]thiazol-2-yl) acetonitrile and bis(benzo[]thiazol-2-yl) methane, respectively. The compounds were thoroughly characterized by using HR-MS, 1D and 2D NMR spectroscopy, and X-ray crystallography for two compounds.

Synthesis of Acenaphthene Fused Dithiaporphyrin(3.1.1.1)s and N-Fused Triphyrin(3.1.1)s in One-Pot Condensation.

Two different types of novel nonaromatic acenaphthene fused macrocycles such as acenaphthene fused dithiaporphyrin(3.1.1.

Pyrrolizinofluorene-embedded dithiacalixcorrole(1.0..)s.

An unprecedented synthesis of pyrrolizinofluorene moiety embedded dithiacalixcorrole(1.0..

Synthesis of anthracene-bridged expanded rosarin.

The newly synthesized precursor 1,8-di(1-pyrrol-2-yl)anthracene was condensed with pentafluorobenzaldehyde under acid-catalyzed conditions to afford the first example of a unique anthracenyl-bridged rosarin. The X-ray structure revealed a coil-like arrangement of three dipyrromethene moieties and three anthracenyl units in the rosarin framework, which exhibits a weak fluorescence at 676 nm.

Synthesis of pyridyl functionalized 3-pyrrolyl BODIPY based fluoroprobes and application towards highly selective detection of picric acid.

A series of pyridyl-coupled 3-pyrrolyl BODIPY fluoroprobes were synthesized by varying the position of the pyridyl/-methylated pyridyl group at the α-/-position of the 3-pyrrolyl BODIPY scaffold and thoroughly characterized by HRMS and 1D/2D NMR techniques. Our studies indicated that only the water-soluble -methylated -pyridyl 3-pyrrolyl BODIPY among various pyridyl-coupled 3-pyrrolyl BODIPYs synthesized here showed an effective and exclusive sensing for picric acid (HPA). The -methylated -pyridyl 3-pyrrolyl BODIPY rapidly detects HPA in an aqueous medium with exceptional selectivity, sensitivity (LOD = 7.

Synthesis, Structure, Spectral, Redox, and Theoretical Studies of Sterically Crowded Decaaryl Triphyrin(2.1.1)s.

First examples of sterically crowded β- and meso-arylated decaaryl triphyrin(2.1.1)s were synthesized by reacting β-hexabromo meso-tetraaryl triphyrin(2.

Synthesis of triphyrin(2.1.1)-triphyrin(2.1.1) homo dimers and bis-Re(I) triphyrin dimer complex.

First examples of covalently linked triphyrin(2.1.1)-triphyrin(2.

An efficient learning based approach for automatic record deduplication with benchmark datasets.

With technological innovations, enterprises in the real world are managing every iota of data as it can be mined to derive business intelligence (BI). However, when data comes from multiple sources, it may result in duplicate records. As data is given paramount importance, it is also significant to eliminate duplicate entities towards data integration, performance and resource optimization.

Synthesis and studies of covalently linked (BODIPY)-3-pyrrolyl BODIPY triads.

Two novel covalently linked triads containing one 3-pyrrolyl BODIPY unit and two BODIPY units were synthesized over a sequence of steps using -(-formylphenyl)-3-pyrrolyl BODIPY as a key precursor. Both triads were thoroughly characterized and studied by using HRMS, 1D and 2D NMR spectroscopy, X-ray crystallography, absorption, steady-state and time-resolved fluorescence, cyclic voltammetry, and DFT/TD-DFT techniques. X-ray structural analysis of these triads revealed that the dipyrrin units of both -BODIPY and 3-pyrrolyl BODIPY were oriented in the same plane whereas the dipyrrin unit of the α-BODIPY unit was oriented almost perpendicular to that of the 3-pyrrolyl BODIPY unit.

Abundance and age structure of critically endangered long-billed () and white-rumped () vultures at the breeding colonies of Kaghaznagar Forest Division and its adjoining areas in the Deccan Plateau, India.

Kaghaznagar and Sironcha Forest Divisions in the Deccan Plateau of India support large breeding colonies of critically endangered species of long-billed (LBV) and white-rumped (WRV) vultures. To assess their abundance and age-structure, that are important population parameters, they were surveyed every month at their breeding colonies; LBV at Palarapu cliff during 2010-2021 and Lakkameda cliff during 2015-2021, and WRV at Dechilpeta during 2014-2021. Breeding colonies of LBV supported a mean of 32 ± 1.

Phenothiazine Embedded Dithiasmaragdyrins.

Two different types of novel phenothiazine-embedded dithiasmaragdyrins containing one phenothiazine ring, two thiophene rings and two pyrrole rings connected via three meso carbons and two direct bonds in the macrocyclic framework were synthesized over the sequence of synthetic steps starting with phenothiazine. Three examples of phenothiazine-embedded dithiasmaragdyrins were synthesized by condensing appropriate phenothiazine-based pentapyrrane with pentafluorobenzaldehyde and two examples of phenothiazine sulfone embedded dithiasmaragdyrins were synthesized by condensing phenothiazine-based diol with appropriate meso-aryl dipyrromethane under mild acid-catalysed conditions. 1D&2D NMR studies revealed that the thiophene rings adopted inverted orientation in phenothiazine sulfone embedded dithiasmaragdyrins whereas in phenothiazine-embedded dithiasmaragdyrins, the thiophene rings were in normal orientation.

Porphyrinoid framework embedded with polycyclic aromatic hydrocarbons: new synthetic marvels.

The highly conjugated tetrapyrrolic porphyrin macrocycle and its contracted and expanded congeners have been extensively used for a wide range of applications across diverse research domains because of their captivating and intriguing features. Over the years, the porphyrin framework and electronic properties of porphyrinoids have been modified and tuned by replacing one or more pyrrole ring(s) with five- and six-membered heterocycles/carbacycles, and their resulting properties have been explored. In recent times, polycyclic aromatic hydrocarbons (PAHs), such as biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, fluorene, pyrene and dibenzo[,]chrysene, have been used to replace one or more pyrrole rings of porphyrinoids, and resulting polycyclic-aromatic-embedded porphyrinoids show unique features that differ from those of other modified porphyrinoids.

Near-infrared absorbing nonaromatic core-modified -benzicalixhexaphyrin(1...1.1.1)s.

Stable nonaromatic core-modified -benzicalixhexaphyrins containing one -phenylene ring, four pyrrole rings and one heterocyclic ring such as furan, thiophene, selenophene and telluorophene connected four -sp carbons and two -sp carbons in a macrocyclic framework were synthesized. The -benzitripyrrane dicarbinol was condensed with 16-heterocycle tripyrranes under mild acid-catalyzed and inert conditions followed by open-air oxidation with DDQ to obtain macrocycles in 2-5% yields. The presence of two -OH groups in the -orientation at two different -sp carbons, which are adjacent to the -phenylene ring of the macrocycle, was confirmed through detailed 1D and 2D NMR studies.

An α-benzithiazolyl 3-pyrrolyl BODIPY probe for ratiometric selective sensing of cyanide ions and bioimaging studies.

A simple chromo-fluorogenic chemodosimeter probe, α-benzithiazolyl 3-pyrrolyl BODIPY, was synthesized by reacting α-formyl 3-pyrrolyl BODIPY with 2-aminothiophenol in DMF at reflux under basic conditions. The probe was structurally characterized by X-ray, HR-MS, and 1D & 2D NMR techniques. The X-ray structure revealed that the appended pyrrole was almost in the plane with a small deviation of 12.

Synthesis and Studies of Symmetrical DitelluraCalix[6]phyrin(1.1.1.1.1.1)s.

Rare examples of ditellura calix[6]phyrin(1.1.1.

Synthesis of unsymmetrical 2,3,7,8-tetrabromo -5,10,11,16-tetraaryl- triphyrin(2.1.1) and its use in the synthesis of sterically crowded 2,3,5,7,8,10,11,16-octaarylated triphyrin(2.1.1)s.

Triphyrin(2.1.1) is a 14π aromatic contracted congener of an 18π aromatic porphyrin(1.

One Pot Synthesis of Two Distinct Macrocycles: Aromatic p-Benzihexaphyrin and Nonaromatic Doubly Fused p-Benzihexaphyrin.

Aromatic trithia p-benzihexaphyrins and nonaromatic doubly fused trithia p-benzihexaphyrins were synthesized in a one pot reaction by condensing a p-benzithiophene based tetrapyrrane with three different bithiophene diols under acid catalyzed conditions. The aromatic and nonaromatic macrocycles showed clear differences in colour, NMR, absorption, and electrochemical properties. Theoretical studies supported the observed aromatic and nonaromatic characteristics, respectively, of the p-benzihexaphyrins and their N-fused derivatives.

Synthesis of Phenothiazine Embedded Heteroporphyrins.

A series of phenothiazine embedded heteroporphyrins containing one phenothiazine unit, two pyrrole rings and one heterocycle such as furan, thiophene, selenophene and tellurophene connected via four meso carbons were synthesized. The macrocycles were synthesized by condensing the phenothiazine based tripyrrane with corresponding 2,5-bis(hydroxymethyl)heterocycle under BF  ⋅ OEt catalyzed conditions and compared the structural, spectral, and electrochemical properties with the reported phenothiazinophyrins. The studies showed that the phenothiazine embedded heteroporphyrins were nonaromatic and electronic properties were significantly altered by replacing the pyrrole ring from phenothiazinophyrin with different heterocycles.

A white light emitting single halochromic hydrazine bridged bis(3-pyrrolyl BODIPY) fluorophore.

In search of white light emitting fluorophores, a hydrazine bridged Schiff base compound, bis(3-pyrrolyl BODIPY), was synthesized by condensing readily available α-formyl 3-pyrrolyl BODIPY with hydrazine hydrate in CHOH under reflux for 5 h followed by recrystallization. Bis(3-pyrrolyl BODIPY) was thoroughly characterized by HR-MS, 1D and 2D NMR, and X-ray crystallography. The X-ray structure revealed that the 3-pyrrolyl BODIPY units in the dyad were arranged to each other with respect to the hydrazine moiety.

Dibenzi Heteroheptaphyrin(2.0.1.1.1.1.0)s: Synthesis, Spectral, Redox and Theoretical Studies.

Three examples of dibenzi heteroheptaphyrin(2.0.1.

Dibenzothiophene-Containing Thiacarbaporphyrinoids.

A new type of expanded dibenzothiophene-containing thiacarbaporphyrinoid containing one dibenzothiophene, two -phenylene, one thiophene, and two pyrrole rings connected via four carbons and two direct bonds was synthesized over a sequence of six steps starting with commercially available dibenzothiophene. The X-ray structure obtained for one of the macrocycles revealed that the macrocycle was very nonplanar and the two -phenylene rings and dibenzothiophene unit were deviated from the mean plane, whereas the thiophene ring attained inverted conformation and was facing toward outside the macrocyclic core. The X-ray structure also revealed that the dibenzothiophene unit of the macrocycle maintained its π-electron delocalization and did not extend the π-electron delocalization with the rest of the macrocycle, and the effective π-conjugation was present only in the lower part of the macrocyclic core, i.

Structural isomers of di--benzidithiaoctaphyrins.

The and structural isomers of di--benzidithiaoctaphyrins were synthesized by adopting two different synthetic routes using readily available precursors under acid-catalyzed conditions, and the isomers were separated using basic alumina column chromatography. 1D and 2D NMR spectroscopy were used to deduce the molecular structures of the macrocycles, which also helps to differentiate the isomer from the isomer. DFT studies revealed that both the and isomers adopt figure of eight conformations but exhibit clear differences in their structural features, and the isomer is more distorted than the isomer.

Synthesis, Structure, Spectral, Electrochemical, and Theoretical Studies of Ru(II) Complexes of 3-Pyrrolyl BODIPY-Based Ligands.

3-Pyrrolyl BODIPY having an appended pyrrolyl group at the 3-position of BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) and its functionalized derivatives have been used as ligands to prepare one example of Ru(II) complex of pyrrolyl dipyrrin and three unique examples of bichromophoric BODIPY-Ru(II) complexes in good yields. The complexes were characterized by HR-MS, 1D and 2D NMR, X-ray analysis for two complexes, absorption, cyclic voltammetry, and DFT/TD-DFT techniques. The X-ray structure of the Ru(II) complex of pyrrolyl dipyrrin revealed that the geometry around the Ru(II) ion was pseudo-octahedral with an arene unit occupying three coordination sites in η-fashion and two nitrogen atoms of the dipyrrin ring and one chloro group adopting the "three legs piano-stool" structure.

Synthesis of stable nonaromatic phenothiazinophyrins.

Stable and nonaromatic phenothiazinophyrins which resulted from the replacement of one of the pyrrole rings of porphyrin with a phenothiazine unit were synthesized by condensing phenothiazine based tripyrrane with aryl aldehyde and pyrrole under acid catalysed conditions. NMR studies revealed that the pyrrole ring that is across the phenothiazine unit is inverted and DFT studies also supported that the pyrrole ring inverted phenothiazinophyrins were more stable. Phenothiazinophyrins and their protonated derivatives showed panchromatic absorption features and absorbed in the visible to NIR region.