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. 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.

Near-infrared absorbing nonaromatic core-modified meta-benzicalixhexaphyrin(1.1.1.1.1.1)s.

Stable nonaromatic core-modified m-benzicalixhexaphyrins containing one m-phenylene ring, four pyrrole rings and one heterocyclic ring such as furan, thiophene, selenophene and telluorophene connected via four meso-sp2 carbons and two meso-sp3 carbons in a macrocyclic framework were synthesized. The m-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 cis-orientation at two different meso-sp3 carbons, which are adjacent to the m-phenylene ring of the macrocycle, was confirmed through detailed 1D and 2D NMR studies. NMR studies indicated that the heterocyclic ring present across the m-phenylene ring prefers to be in the inverted conformation in these macrocycles. The macrocycles exhibited two intense absorption bands in the lower wavelength region of 320-580 nm and one broad absorption band that extended from the visible to NIR region, and the protonated derivatives of such macrocycles showed significant bathochromic shifts to the NIR region. Additionally, the electrochemical studies indicated that the macrocycles underwent easier oxidation due to their electron-rich nature. DFT studies revealed that the macrocycles adopted highly distorted conformation, which was consistent with experimental results.

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[g,p]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. The polycyclic aromatic hydrocarbons in the porphyrinoid macrocyclic framework induce different π-conjugation pathways in macrocycles, exhibit variable degrees of aromaticity from nonaromatic to aromatic and antiaromatic and provide a unique ligand environment to form stable coordination and organometallic complexes in which metals show uncommon oxidation states and unusual reactivity. This review presents an overview of the synthesis, coordination chemistry, structure and properties of various porphyrinoids with an embedded PAH that have been reported to date.

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 12.15° from the 12-atom mean plane of the BF2-dipyrrin core and the benzithiazolyl moiety was also deviated by 18.74° from the BF2-dipyrrin core. The α-benzithiazolyl 3-pyrrolyl BODIPY exhibits one intense absorption band at 608 nm and a less intense band at 412 nm corresponding to the 3-pyrrolyl BODIPY and benzithiazolyl moiety, respectively. The strongly fluorescent probe shows one intense emission band at 637 nm with a quantum yield of 0.48. The probe acted as an exclusive colorimetric and chemodosimetric sensor for CN- ions over other anions with high sensitivity (LOD = 13 nM) and quick response time (10 s) in an aqueous CH3CN medium. The CN- ion attacks the imine group of the benzithiazolyl moiety of 3via a nucleophilic addition reaction and converts the sp2 to sp3 carbon which disrupts the conjugation between the 3-pyrrolyl BODIPY and benzithiazolyl moieties, which is reflected in the clear colour change from red fluorescence to blue fluorescence as well as significant changes in the spectral and electrochemical properties. The detection of cyanide with the probe for biological applications was also performed with plant tissue. DFT/TD-DFT studies were in agreement with the experimental observations.

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

Rare examples of ditellura calix[6]phyrin(1.1.1.1.1.1)s containing two telluratripyrrin units connected via two sp3 carbons were synthesized by condensing 16-telluratripyrrane with a cyclic ketone in CH2Cl2 under acid-catalyzed conditions. The X-ray structure obtained for meso-cyclohexyl-substituted calix[6]phyrin revealed that the macrocycle resembles a roof-like shape with two telluratripyrrin units that are perpendicular to each other, whereas the DFT-optimized structure of meso-cyclopentyl-substituted calix[6]phyrin showed a bird-like structure with two telluratripyrrin units that are almost in the same plane.

Synthesis of unsymmetrical 2,3,7,8-tetrabromo meso-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(1.1.1.1). An unsymmetrical 2,3,7,8-tetrabromo meso-tetraaryl triphyrin(2.1.1) containing four bromides at the ß-pyrrole carbons of two out of three pyrrole rings of the triphyrin core was synthesized for the first time in 90% yield by treating meso-tetraaryl triphyrin(2.1.1) with five equivalents of N-bromosuccinimide in 1,2-dichloroethane (DCE) under reflux for 8 h. The X-ray structure revealed that the triphyrin(2.1.1) macrocycle was significantly distorted in 2,3,7,8-tetrabromo meso-tetraaryl triphyrin compared to planar meso-tetraaryl triphyrin. A series of novel sterically crowded 2,3,5,7,8,10,11,16-octaaryl triphyrin(2.1.1)s were synthesized by coupling 2,3,7,8-tetrabromo meso-tetraaryl triphyrin with six different aryl boronic acids under Suzuki-Miyaura coupling conditions. NMR, absorption, electrochemical and theoretical studies revealed that the structure and electronic properties were drastically altered in the 2,3,5,7,8,10,11,16-octaaryl triphyrin(2.1.1) series due to the presence of four additional aryl groups at the ß-pyrrole carbons which caused steric crowding at the periphery of the triphyrin core resulting in a decrease in effective π-conjugation in the triphyrin(2.1.1)s.

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 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.

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

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 CH2 Cl2 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.

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.

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 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.

Dibenzothiophene-Containing Thiacarbaporphyrinoids.

A new type of expanded dibenzothiophene-containing thiacarbaporphyrinoid containing one dibenzothiophene, two p-phenylene, one thiophene, and two pyrrole rings connected via four meso 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 p-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.e., the thiatripyrrin moiety. The spectral and theoretical studies support the nonaromatic nature of the macrocycles. The macrocycles exhibit one strong absorption band at ∼430 nm and one broad absorption band in the 500-800 nm region, which were bathochromically shifted in diprotonated derivatives which absorb strongly in the visible-NIR region. The electrochemical studies indicated the electron-rich nature of the macrocycles and the theoretical studies corroborated the experimental observations.

Structural isomers of di-p-benzidithiaoctaphyrins.

The cis and trans structural isomers of di-p-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 cis isomer from the trans isomer. DFT studies revealed that both the cis and trans isomers adopt figure of eight conformations but exhibit clear differences in their structural features, and the trans isomer is more distorted than the cis isomer. Experimental and theoretical studies revealed that both the cis and trans isomers are nonaromatic stable macrocycles and show subtle differences in their structure, spectral and redox properties. The cis and trans isomers of di-p-benzidithiaoctaphyrin exhibit nonaromatic absorption features in the visible-NIR region, and electrochemical studies revealed their electron-rich nature. TD-DFT studies are in agreement with the experimental observations.

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.

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 η6-fashion and two nitrogen atoms of the dipyrrin ring and one chloro group adopting the "three legs piano-stool" structure. The X-ray structure of the bichromophoric BODIPY-Ru(II) complex revealed that the BODIPY core was planar and the central B(III) was coordinated with two pyrrole nitrogens of the dipyrrin unit and two axial fluoride ions in a tetrahedral geometry, and Ru(II) was bonded to appended pyrrole "N" and "N" of benzimidazole substituent present at the α-position of appended pyrrole, one chloro group, and one arene ring in a pseudo-octahedral geometry. The spectral studies revealed that the electronic properties of the BODIPY unit in BODIPY-Ru(II) complexes were significantly altered, and electrochemical studies indicated that the BODIPY-Ru(II) complexes exhibit one oxidation corresponding to Ru(II) to Ru(III) and one reduction corresponding to the BODIPY unit. The DFT/TD-DFT studies corroborated the experimental observations.

Synthesis and Properties of Nonaromatic meso-fused Heterobenzihomoporphyrin(2.1.1.1)s.

Fluorene-based tripyrrane has been used as a fused precursor to synthesize three novel examples of nonaromatic meso-fused thia and selenabenzihomoporphyrin(2.1.1.1)s by condensing it with appropriate 2,5-bis(hydroxymethyl)aryl thiophene or selenophene under acid catalyzed conditions. The meso-fused heterobenzihomoporphyrins contain one fluorene unit, two pyrrole rings and one thiophene/selenophene ring connected via five meso-carbons in the macrocyclic framework. The macrocycles were thoroughly characterized by HR-MS, 1D and 2D NMR, absorption, cyclic voltammetry and DFT/TD-DFT studies. NMR, absorption, and DFT studies indicated the nonaromatic nature of meso-fused heterobenzihomoporphyrins. The macrocycles displayed one intense band at ∼380 nm along with a shoulder band at 450 nm and a broad band in the region of 590-850 nm which were bathochromically shifted in the monoprotonated derivatives and absorbed prominently in the NIR region with the peak maxima at ∼1035 nm. The electrochemical studies revealed that the macrocycles showed three well-defined oxidations and reductions, and TD-DFT studies corroborated experimental observations.

Anthriporphyrinoids: Design, Synthesis, and Reactivity towards Diels-Alder Reaction.

A series of non-aromatic anthripentaphyrins containing an anthracene unit, two thiophenes, and two pyrrole rings as a part of a macrocyclic framework connected via three meso-carbons were synthesized. The crystal structure of one of the anthripentaphyrins revealed that the two thiophene rings were in an inverted orientation, and the macrocycle adopts a nonplanar Z-like ruffled structure. These anthriporphyrinoids act as dienes and undergo Diels-Alder reaction with dienophiles to form stable non-aromatic Diels-Alder adducts.

Synthesis, Spectral, Redox and Theoretical Studies of Stable Nonaromatic Dicarba Dithia Hexaphyrin(2.0.1.1.1.0)s with Two Inverted Thiophenes.

A series of dicarba dithia hexaphyrin(2.0.1.1.1.0)s containing two p-phenylene rings, two thiophene rings, and two pyrrole rings connected via five meso carbons were synthesized by condensing the key precursor, hexapyrrane, which was prepared over a sequence of steps, with the appropriate aromatic aldehyde under acid catalytic conditions followed by alumina chromatographic purification. Detailed one-dimensional (1D) and two-dimensional (2D) NMR studies revealed that the two thiophene rings were inverted and facing outward from the macrocyclic core. Interestingly, one of the inverted thiophene rings adopts a normal orientation in the protonated derivatives of macrocycles generated by addition of trifluoroacetic acid to the appropriate macrocyclic solution. The spectroscopic studies support the non-aromatic nature of macrocycles, and the macrocycles exhibit a distinct sharp band at ∼425 nm along with a broad band in the range of 550-1000 nm, which experienced a red shift with a clear color change in the protonated derivatives. The redox studies showed lower oxidation potentials, indicating their electron-rich nature. The density functional theoretical (DFT) studies showed that the hexaphyrins adopt oval-shaped structures, and time-dependent-DFT (TD-DFT) studies parallelly matched the experimental observations of macrocycles.

Synthesis and Studies of Mono-functionalized Telluradithiasapphyrins and Covalently Linked Porphyrin- Telluradithiasapphyrin Dyads.

A series of mono-functionalized aromatic 22π telluradithiasapphyrins containing functional groups such as p-bromophenyl, p-iodophenyl, p-nitrophenyl and p-trimethylsilylethynyl phenyl groups at one of the meso-positions were synthesized by condensing appropriately functionalized unsymmetrical bithiophene diol and 16-telluratripyrrane in CH2 Cl2 under acid-catalyzed conditions. To demonstrate the reactivity of mono-functionalized telluradithiasapphyrins, we synthesized the first examples of covalently linked diphenyl ethyne bridged four novel 18π porphyrin/metalloporphrin-22π telluradithiasapphyrin dyads by coupling meso-ethynyl phenyl porphyrin with telluradithiasapphyrin containing meso-iodophenyl group under Pd(0) coupling conditions followed by metalation of porphyrin unit by treating free base dyad with appropriate metal salts. The dyads were characterized and studied by mass, 1D & 2D NMR, absorption, cyclic voltammetry, fluorescence and DFT techniques. The DFT analysis showed that the porphyrin/metalloporphyrin and sapphyrin units in dyads orient with each other in different angles and Zn(II) porphyrin-sapphyrin dyad (Zn-dyad) showed minimum whereas the free base dyad showed maximum angle of deviation. NMR, absorption, and redox studies indicated that the dyads exhibit the overlapping features of their constituted monomers and maintain their individual characteristic features. The steady-state fluorescence studies revealed that the fluorescence of the porphyrin/metalloporphyrin unit was significantly quenched due to possible energy/electron transfer from the porphyrin/metalloporphyrin unit to non-emissive sapphyrin unit in dyads.

Tuning of Heterocyclic Ring in Para-Benzi Heterosapphyrins.

Three examples of moderately aromatic p-benzi dithiasapphyrin and p-benzi tellurathiasapphyrins have been synthesized by condensing p-benzithiophene diol with 16-thia/telluratripyrrane under acid-catalyzed reaction conditions. The X-ray structural analysis showed that the thiophene ring in p-benzi dithiasapphyrin was inverted, whereas the tellurophene ring in p-benzi tellurathiasapphyrins was normal conformation with respect to the macrocyclic core. However, NMR studies revealed that the thiophene ring in protonated p-benzi dithiasapphyrin flips to normal, whereas the tellurophene ring in p-benzi tellurathiasapphyrins flips to inverted orientation.

Pd(II), Ni(II), and Cu(II) complexes of α,α'-ditolylmethanone dipyrroethene.

Dipyrromethenes containing two pyrrole rings connected by one meso-carbon are versatile monoanionic bidentate ligands and form coordination complexes with many metals/nonmetals/metalloids. Dipyrroethenes containing one additional meso-carbon compared to dipyrromethenes have more space between coordinating pyrrole nitrogens and provide a good coordination environment but have not been explored as ligands in coordination chemistry. Dipyrroethenes are dianionic bidentate ligands and by suitable modifications, the coordination environment of dipyrroethenes can be changed further. Herein, we successfully synthesized α,α'-ditolylmethanone dipyrroethene which is a bipyrrolic tetradentate ligand with an ONNO ligand core and used it for the synthesis of novel Pd(II), Ni(II), and Cu(II) metal complexes by treating it with respective metal salts in CH2Cl2/CH3OH at room temperature. The X-ray crystallographic structure of the metal complexes showed that the M(II) ion was coordinated to the ONNO atoms of the ligand in a perfect square planar geometry. The NMR studies of Pd(II) and Ni(II) complexes also supported the highly symmetric nature of the metal complexes. The absorption spectra of the metal complexes showed strong bands in the region of 300-550 nm. The electrochemical studies of metal complexes revealed that only ligand-based oxidation and reduction were observed. The DFT and TD-DFT studies were in agreement with the experimental observations. Our preliminary studies indicated that the Pd(II) complex can be used as a catalyst for the Fujiwara-Moritani olefination reaction.