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.

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.

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.

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 of Benzofuran-Embedded Selena- and Telluraporphyrins.

The benzofuran-embedded selena- and telluraporphyrins are resulted by replacing the pyrrole ring that is across the selenophene/tellurophene ring in meso-tetraaryl 21-selenaporphyrin and 21-telluraporphyrin respectively by a benzofuran unit. Three examples of benzofuran-embedded selenaporphyrins and one example of benzofuran-embedded telluraporphyrin were synthesized by adopting a simple 3 + 2 synthetic protocol involving the condensation of benzofuran based tripyrrane with appropriate 2,5-bis(hydroxymethylaryl) selenophene/telluorophene to afford pure benzofuran-embedded selenaporphyrins and telluraporphyrin in 3-6% yields. The macrocycles were thoroughly characterized and studied by various spectroscopic and computational techniques. The spectral and computational studies certified their nonaromatic nature unlike aromatic meso-tetraaryl 21-selena/21-telluraporphyrins, which proves that replacement of pyrrole with a benzofuran ring results in complete alteration of electronic properties. The DFT studies revealed that the benzofuran moiety hinders π-electron delocalization in the macrocycle due to its inflexibility, and the macrocycles adopt highly deformed saddle-shaped structures. The absorption spectra of benzofuran-embedded selena- and telluraporphyrins showed one strong band at ∼350-380 nm and one broad band at ∼650-695 nm that extended up to ∼900 nm. However, the protonated derivatives of macrocycles absorb strongly in the NIR region with a band trailing up to 1200 nm. The electrochemical studies revealed that the macrocycles are electron deficient, and theoretical studies resembled the 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 Fused Benzo-Benzisapphyrins.

A series of rare examples of fused benzo-benzisapphyrins were synthesized readily by (3 + 2) condensation of benzodipyrrole-derived diol and para-benzitripyrrane in the presence of 0.5 equiv of TFA in CH2Cl2 under inert atmosphere conditions accompanied by DDQ oxidation in open air. The crude compounds were separated by basic alumina column chromatography and afforded pure fused benzo-benzisapphyrins in 20-22% yields. The fused sapphyrins were characterized in detail by high-resolution mass spectrometry (HRMS) and one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy. The 1H NMR spectra recorded at both 298 and at 233 K clearly exhibited the presence of a strong diatropic ring current in benzo-benzisapphyrins, and the macrocycles are of aromatic nature. The DFT-optimized structure of benzo-benzisapphyrin revealed that the macrocycle was planar to a great extent due to the rigid structure of the dibenzopyrrole moiety, and the NICS(0) value of -11.2 ppm supports the aromatic nature of macrocycles. The absorption spectra of benzo-benzisapphyrins showed three weak Q bands approximately in the region of 650-900 nm and a strong Soret band at 480 nm, along with a shoulder band at ∼510 nm. The diprotonated derivative generated by the addition of excess TFA to the benzo-benzisapphyrin macrocycle exhibited bathochromically shifted absorption bands compared to the free base macrocycle.

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.

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.

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.

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.

Synthesis and Properties of Stable 20π Porphyrinoids.

The 20π porphyrinoids are immediate higher homologues of 18π porphyrins and differ from porphyrins in aromaticity which in turn affects the structure, properties and chemical reactivities. Research over the years indicated that the 20π porphyrinoids can be stabilized as non-aromatic/anti-aromatic or Mobius aromatic macrocycles using different strategies such as core-modification of porphyrins, non-metal/metal complexation of porphyrins, peripheral modification of porphyrins and expanded porphyrinoids. The structural properties such as aromaticity of the macrocycle can be controlled by choosing the right synthetic strategy. This review will provide an overview of the development in the chemistry of 20π porphyrinoids giving emphasize on the synthesis, structure and electronic properties of these macrocycles which have huge potential for various applications.

Bis-(Fluorene)-Embedded Hexaphyrins.

The polyaromatic hydrocarbon containing expanded porphyrins, bis-(fluorene)-embedded hexaphyrins, were synthesized by condensing fluorene-based tripyrrane with pentafluorobenzaldehyde in CH2Cl2 in the presence of 1 equiv of BF3·OEt2 under an inert atmosphere followed by oxidation with DDQ in open air at room temperature. The reaction worked only when 1 equiv of BF3·OEt2 was added to the reaction mixture under concentrated reaction conditions. The bis-(fluorene)-embedded macrocycles were characterized and studied by high-resolution mass spectrometry (HRMS), nuclear magnetic resonance (NMR), absorption, electrochemical, and density functional theory (DFT)/time-dependent (TD)-DFT techniques. In 1H NMR, the hexaphyrins showed a few broad unresolved resonances at room temperature, but the NMR spectra were well-resolved at lower temperatures, indicating that the hexaphyrins were very flexible. The DFT-optimized structures indicated that the two fluorene units at the crossing point of the figure-eight loop makes an angle of ∼79.73° with each other, the fluorene moieties maintained their own planarity, and one of the fluorene moieties was not involved in conjugation with the rest of the macrocycle. The absorption spectra of hexaphyrins showed one intense sharp band in the higher energy region and a broad band in the lower energy region. The electrochemical studies indicated that expanded hexaphyrins are relatively electron-rich and showed three easier oxidations and one reduction. The DFT/TD-DFT studies are in agreement with the experimental observations.

Synthesis of Doubly Fused Phenothiazine-Embedded Dithiasapphyrins.

The condensation of phenothiazine-based tripyrrane with bithiophene diol in the presence of acid catalysts resulted in the formation of unique doubly fused phenothiazine-embedded dithiasapphyrins instead of the expected nonfused phenothiazine-embedded dithiasapphyrins. Four examples of different meso-substituted N-C-fused dithiasapphyrins were synthesized to demonstrate the versatility of the (3 + 2) condensation reaction. High-resolution mass spectrometry and different spectroscopic and computational techniques were used to confirm the intramolecular ring fusion in our reported macrocycles. DFT studies showed that the double N-C-fused dithiasapphyrins were thermodynamically more stable as opposed to the nonfused phenothiazine-embedded dithiasapphyrin. The nonaromaticity in the macrocycles was established with the help of NMR, absorption, and DFT studies. The absorption spectra showed distinct bands in the visible region which were bathochromically shifted to the NIR region after protonation. The electrochemical studies revealed the highly electron-rich nature of the macrocycles, and theoretical studies were similar to the experimental observations.

Vacatadithiasapphyrins: Synthesis, Structure, and Spectral and Redox Properties.

Four examples of novel aromatic [22]vacatadithiasapphyrins were synthesized by refluxing appropriate [22]telluradithiasapphyrins in 1,2-dichlorobenzene in the presence of excess HCl followed by simple column chromatographic purification. The [22]vacatadithiasapphyrins can exist in three conformers "in", "out", and "zigzag" w.r.t the butadiene moiety, and under our experimental conditions, the "out" conformer was the major compound. The X-ray structure obtained for one of the "out" conformers of vacatadithiasapphyrins revealed that the macrocycle was planar similar to its parent telluradithiasapphyrin and showed effective π-delocalization over the entire macrocyclic core. NMR studies supported the formation of the "out" conformer and suggested that the vacatadithiasapphyrins were less aromatic than the parent telluradithiasapphyrins. Density functional theory, time-dependent DFT, and nuclear independent chemical shift studies indicated that the protonated form of vacatadithiasapphyrin was more aromatic than the parent protonated telluradithiasapphyrin. The absorption spectra of vacatadithiasapphyrins showed a typical strong Soret band at ∼488 nm and four relatively broad Q-bands in the region of 590-860 nm, and electrochemical studies suggest that vacatadithiasapphyrins were easier to oxidize and easier to reduce compared to the parent telluradithiasapphyrins.

Synthesis and Studies of Core-Modified Tellura Dithiasapphyrins.

Four different aromatic meso-substituted tellurophene-containing dithiasapphyrins were synthesized by acid-catalyzed [3+2] condensation of 16-telluratripyrrane with bithiophene diol in 22-23% yields. The structural, spectral, and electrochemical properties of tellura dithiasapphyrins were studied and compared with those of previously reported aza (pyrrole)- and other heterocycle (furan, thiophene, and selenophene)-containing dithiasapphyrins. Nuclear magnetic resonance studies indicated that the tellurophene ring in tellura dithiasapphyrins is in the normal conformation, facing toward the inner core, but flips in diprotonated derivatives to an inverted conformation, facing away from the macrocyclic core, unlike aza- and other heterocycle-containing dithiasapphyrins in which pyrrole and the corresponding heterocycle ring always prefer to be in inverted conformation in their neutral and protonated forms. The crystal structure obtained for one of the tellura dithiasapphyrins showed that the macrocycle is highly planar and the tellurophene ring is in the normal conformation. The absorption spectra of tellura dithiasapphyrins exhibited slight hypsochromic shifts compared to those of pyrrole- and other heterocycle-containing dithiasapphyrins. The redox studies indicated that the tellura dithiasapphyrins are electron deficient and readily undergoes reductions. Density functional theory and nuclear independent chemical shift studies indicated that the macrocycles are aromatic, and the computational results closely matched the experimental observations.

Doubly Fused Unsymmetrical Calixdicarbahexaphyrins.

Three novel doubly fused unsymmetrical calixdicarbahexaphyrins were synthesized by mild acid-catalyzed (4+2) condensation of dicarbatetrapyrrane with dipyrroethene diol followed by oxidation. The condensation formed doubly fused calixdicarbahexaphyrins instead of π-conjugated dicarbahexaphyrins, due to the unusual fusion of the pyrrole N with the α-carbon of the adjacent pyrrole ring to form a tripentacyclic ring and one usual fusion of the pyrrole N with the adjacent phenylene C to form a fused moiety containing two pentacycles and one hexacycle ring. Both fusions occurred on one side of the macrocycle, making the macrocycles unsymmetric. The crystal structure obtained for one of the macrocycles exhibited a saddle-shaped structure with two benzene rings and four pyrrole rings connected via two ethylene and four methene meso-carbon atoms. The crystal structure also revealed unusual fusions in the macrocyclic framework and the presence of one sp3 carbon that disrupts the π-electron delocalization. 1H, 1H-1H COSY, NOESY, 13C, and HMBC NMR techniques were used to characterize the macrocycles. The absorption spectra of the macrocycles showed one intense sharp band at ∼485 nm along with a shoulder in the lower-energy region, suggesting its non-aromatic nature. Electrochemical studies indicated their electron rich nature, and DFT/TD-DFT studies corroborated the experimental observations.