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Calix[n]porphyrinoids containing both sp2 and sp3meso‐carbons can bind metals like porphyrinoids and anions like calix[n]pyrroles. Thus, calix[n]porphyrinoids are hybrid macrocycles of porphyrinoids and calix[n]pyrroles. The core‐modified calix[n]porphyrinoids resulted by replacing one or more pyrroles of calix[n]porphyrinoids with different heterocycles or carbacycles that possesses very attractive structural, spectral, and coordination properties. For the past two decades, several different types of core‐modified calix[n]porphyrinoids in which one or more pyrroles were replaced with other heterocycles such as thiophene, selenophene, tellurophene, silole, phosphole, pyridine, etc and carbacycles such as m/p‐phenylene have been synthesized and explored their structure, metal coordination and anion sensing properties. This review describes different synthetic strategies used for the synthesis of various types of core‐modified calix[4]phyrins and expanded calix[n]phyrins and discusses their key structural aspects, properties, coordination chemistry and applications. [ABSTRACT FROM AUTHOR]

A series of pyridyl-coupled 3-pyrrolyl BODIPY fluoroprobes were synthesized by varying the position of the pyridyl/N-methylated pyridyl group at the α-/meso-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 N-methylated p-pyridyl 3-pyrrolyl BODIPY among various pyridyl-coupled 3-pyrrolyl BODIPYs synthesized here showed an effective and exclusive sensing for picric acid (HPA). The N-methylated p-pyridyl 3-pyrrolyl BODIPY rapidly detects HPA in an aqueous medium with exceptional selectivity, sensitivity (LOD = 7.90 pM), and high binding affinity (Ka = 4.94×108 M-1) through both chromogenic and fluorogenic signalling modes. Our studies support the formation of a charge transfer complex between cationic N-methylated p-pyridyl 3-pyrrolyl BODIPY and picrate as verified by absorption, fluorescence, electrochemical, and NMR techniques. DFT and TD-DFT studies further support the structural and experimental observations, including the sensing mechanism of HPA. [ABSTRACT FROM AUTHOR]

First examples of covalently linked triphyrin(2.1.1)-triphyrin(2.1.1) homo dimers connected via flexible alkoxy linkers at β-pyrrole positions were synthesized in 28–30% yields by reacting 2-bromo triphyrin(2.1.1) with three different alkane diols such as 1,2-ethanediol, 1,4-butanediol and 1,6-hexanediol in toluene under Pd2(dba)3/DPEphos catalyzed conditions by refluxing for 12–20 h. One of the free base triphyrin–triphyrin homo dimers was metallated by treating the homo dimer with Re(CO)5Cl in toluene under reflux and afforded bis-Re(I) homo dimer complex in 53% yield. Three free base homo dimers and one bis-Re(I) homo dimer complex were thoroughly characterized and studied using HR-MS, 1D and 2D NMR, absorption spectroscopy, cyclic voltammetry and DFT calculations. Our attempts to obtain the X-ray structure of homo dimers were not successful. However, DFT studies revealed that homo dimers prefer to exist in anti-conformation rather than syn-conformation and both triphyrin macrocycles in homo dimers were similar in terms of the deviation of pyrrole rings from the mean plane defined by the four meso carbons of the respective triphyrin unit. Absorption spectra of homo dimers showed similar absorption features such as in triphyrin(2.1.1) with slight changes in their absorption peak maxima. Electrochemical studies revealed that the homo dimers were electron rich, whereas the bis-Re(I) complex was electron deficient in nature. [ABSTRACT FROM AUTHOR]

Two novel covalently linked triads containing one 3-pyrrolyl BODIPY unit and two BODIPY units were synthesized over a sequence of steps using meso-(p-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 meso-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. Both triads showed two well-separated absorption bands corresponding to BODIPY and 3-pyrrolyl BODIPY units in the 510–675 nm region. In these triads, the BODIPY unit absorbs in the higher energy region and acts as an energy donor whereas the 3-pyrrolyl BODIPY unit absorbs in the lower energy region and acts as an energy acceptor. Steady-state and time-resolved fluorescence studies of these triads indicated the possibility of intramolecular singlet–singlet energy transfer with almost 98% efficiency from the BODIPY units to the 3-pyrrolyl BODIPY unit upon selective excitation of the BODIPY unit in both triads. DFT and TD-DFT investigations corroborated the experimental findings. [ABSTRACT FROM AUTHOR]

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. Both types of macrocycles exhibit nonaromatic absorption features and showed panchochromic absorption features in its neutral and protonated forms. The electrochemical studies indicated that the phenothiazine‐embedded dithiasmaragdyrins were more electron‐rich compared to phenothiazine sulfone embedded dithiasmaragdyrins. DFT studies revealed that both types of dithiasmaragdyrins exhibit significantly distorted structures and TD‐DFT studies support the experimental observations. [ABSTRACT FROM AUTHOR]

Three new examples of covalently linked bis(3-pyrrolyl BODIPY)s were prepared as key precursors for the synthesis of rare hexapyrrolic ligands by treating readily available 3-pyrrolyl BODIPY with different ketones under acid-catalyzed conditions. The new bis(3-pyrrolyl BODIPY) complexes were thoroughly characterized using HR-MS, NMR spectroscopy, absorption, fluorescence, electrochemistry, and theoretical methods. The bis(3-pyrrolyl BODIPY) complexes were treated with AlCl3 in CH3OH at reflux for 2 h to demask BF2 units to afford novel hexapyrrolic ligands. The hexapyrrolic ligands without isolating were treated with Zn(CH3COO)2 in CH3CN at room temperature for 2 h followed by repeated recrystallization to afford crystalline bis-Zn(II) complexes. The X-ray crystallographic structure obtained for one of the bis-Zn(II) complexes revealed that it was a double-stranded bimetallic helicate containing two non-superimposable M and P enantiomers in equal amounts, which were nonseparable. Each Zn(II) ion in the bis-Zn helicate complexes was coordinated to four nitrogen atoms of two dipyrrin units from two hexapyrrolic ligands in a distorted tetrahedral geometry. The distance between two Zn(II) ions (Zn1–Zn2) in bis-Zn(II) helicate was 8.211 Å, which was longer than the distance between two Cu(II) ions (Cu1–Cu2) in our previously reported bis-Cu(II) helicate complex (7.330 Å). NMR studies indicated that the bis-Zn(II) complexes were highly symmetric. The bis-Zn(II) helicates showed broad absorption bands in the region of 400–700 nm and were nonfluorescent. DFT/TD-DFT studies were in agreement with the experimental observations. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 BF3 ⋅ OEt2 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. The X‐ray structure of phenothiazine embedded thiaporphyrin revealed that the macrocycle was distorted with an inverted thiophene ring. Both mono‐protonated and diprotonated derivatives of macrocycles were generated by the controlled addition of trifluoroacetic acid to the macrocycles. The macrocyclic protons experienced upfield/downfield shifts in protonated derivatives compared to their corresponding neutral phenothiazine embedded heteroporphyrins. However, the heterocyclic ring in both mono‐ and diprotonated derivatives retained its inverted conformation. The macrocycles in their neutral and protonated form exhibit nonaromatic absorption features. The studies indicated the electron rich nature of macrocycles and DFT/TD‐DFT studies were carried out to justify the experimental observations. [ABSTRACT FROM AUTHOR]

This article provides an overview of the synthesis and applications of functionalized aza-BODIPYs, which are fluorescent dyes used in materials, biology, and medicine. Aza-BODIPYs have a nitrogen atom instead of a carbon atom, resulting in different electronic properties. The article discusses different synthetic routes for functionalized aza-BODIPYs and their use in fluorescence systems. It also explores the potential applications of these compounds in gas therapy, photothermal therapy, and biological imaging. The authors emphasize the need for further research in this field. [Extracted from the article]

Three examples of dibenzi heteroheptaphyrin(2.0.1.1.1.1.0)s were synthesized by condensing bis(phenylene ethene) based hexapyrrane with appropriate diol, 2,5‐bis(α‐hydroxy‐α‐arylmethyl) thiophene or selenophene in CH2Cl2 under BF3 ⋅ OEt2 catalyzed inert atmosphere conditions followed by DDQ oxidation in open air. HR‐MS analyses confirmed the identities of dibenzi heteroheptaphyrins. The DFT optimized structures revealed that dibenzi heteroheptaphyrins were highly distorted nonplanar macrocycles with two thiophene rings preferred to be in an inverted conformation. 1D & 2D NMR helped in deducing the molecular structures of dibenzi heteroheptaphyrins and supported their nonaromatic nature. The theoretical NMR calculations were carried which matched closely with the experimental NMR data. NMR studies also revealed that the π‐delocaliztion was significantly altered in dibenzi heteroheptaphyrins compared to previously reported dibenzi hexaphyrins. The dibenzi heptaphyrins showed one sharp absorption band in 400–500 nm region and a broad band in the region of 600–800 nm which were bathochromically shifted in their diprotonated derivatives. The theoretical absorption calculations corroborate the slight hypsochromic shift of the broad absorption band in the lower energy region of dibenzi heptaphyrins compared to dibenzi hexaphyrins. The electrochemical studies revealed that the dibenzi heptaphyrins were easier to reduce but difficult to oxidize compared to dibenzi hexaphyrins. [ABSTRACT FROM AUTHOR]

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 CH3OH 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 trans to each other with respect to the hydrazine moiety. Bis(3-pyrrolyl BODIPY) showed absorption bands in the region of 390–705 nm and exhibited multiple fluorescence bands in the region of 395–720 nm at different excitation wavelengths. The protonated derivative of bis(3-pyrrolyl BODIPY) generated by the addition of TFA to its CH2Cl2 solution showed significant changes in the optical properties and generated white fluorescence under UV light with specific emission bands observed in blue, green, and red regions, indicating that bis(3-pyrrolyl)BODIPY is a single white light emitting halochromic fluorophore under acidic conditions. DFT and TD-DFT studies justify the structural and electronic properties of the protonated derivative of bis(3-pyrrolyl BODIPY) exhibiting white light emission. [ABSTRACT FROM AUTHOR]