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.

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.

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 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.

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.

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.

Synthesis of Pyridine-Containing Crowned Fused Expanded Porphyrins.

New examples of nonaromatic fused expanded porphyrins containing both pyridine and crown ether moiety as a part of macrocyclic framework were synthesized by condensing pyridine based pentapyrrane with polyether-based diol in CH2 Cl2 in the presence of one equivalent of BF3 ⋅ OEt2 under inert conditions followed by oxidation with DDQ in open air. The condensation was expected to form pyridine-containing crowned expanded porphyrins but resulted in the formation of fused crowned expanded porphyrins due to intramolecular fusion of two pyrrole nitrogens with two adjacent inverted thiophene carbons as revealed by X-ray crystallography obtained for one of the macrocycle. HRMS and NMR studies supported the formation of fused crowned pyridine containing expanded porphyrins, and the macrocycles showed simple, well-resolved NMR spectra where all resonances were identified easily by 2D NMR spectroscopy. The macrocycles exhibited typical nonaromatic absorption features and showed one broad band with peak maxima at 535 nm and one or two shoulder bands in the higher energy region. The protonation studies resulted in clear colour change from purple to blue and absorption bands experienced bathochromic shifts with a broad band at 662 nm which was extended up to 800 nm. The electrochemical studies revealed that the macrocycles were easier to oxidize but difficult to reduce. DFT studies indicated that the macrocycle attains a very puckered and distorted 'U' shaped structure owing to the flexibility of the crown ether chain and TD-DFT studies corroborated experimental results. The preliminary studies indicated that the macrocycles could be used as colorimetric optical sensor for the detection of Cu2+ ion.

Phenothiazine-Embedded Hexaphyrins.

Unprecedented nonaromatic stable phenothiazine-embedded porphyrinoids were synthesized by incorporating phenothiazine subunits into the hexaphyrin framework. The crystal structure revealed that the macrocycle adopted a twisted conformation wherein the phenothiazine units maintained their planarity, which was an impediment in π-delocalization throughout the macrocyclic core. The macrocycles exhibited distinct absorption bands in the visible-near-infrared region, and electrochemical studies indicated their electron-rich nature. Theoretical studies were consistent with the experimental observations.

Synthesis and Structural Properties of NIR-Absorbing Pyridine-Containing Heptaphyrins.

Four examples of stable nonaromatic pyridine containing heteroheptaphyrins (pyrithiaheptaphyrins) 2-5 were synthesized in 8-13% yields by [5+2] condensation of newly synthesized pyridine-based pentapyrrane 8 and bithiophene diol 9 a-d. The X-ray crystallographic analysis of macrocycle 2 proved that the macrocycle assumes a highly planar structure with two inverted thiophene rings. The heteroheptaphyrins 2-5 are asymmetric and showed a greater number of resonances in 1 H NMR spectra compared to our previously reported symmetric heterohexaphyrin (pyrithiahexaphyrin) 1 c. Most of the macrocyclic core protons in pyrithiahepaphyrins 2-5 experienced upfield/downfield shifts compared to pyrithiahexaphyrin 1 c indicating the alteration of π-conjugation in the macrocycles. The absorption bands were significantly red-shifted and located in the NIR region in macrocycles 2-5 compared to 1 c supporting the increase of π-delocalization. The theoretical studies support the experimental findings and NICS(0) value supports the non-aromaticity of the macrocycles.

Synthesis, Structure, Spectral, and Anion Sensing Studies of an Aromatic meso-Fused Boron(III) Benzitriphyrin(2.1.1) Complex.

An aromatic tricoordinated organo B(III) complex of benzitriphyrin(2.1.1) was synthesized by treating the nonaromatic phlorin analogue of meso-fused benzitriphyrin(2.1.1) with BCl3 in triethylamine/toluene and refluxing for 2 h. The X-ray structure revealed that B(III) was in a trigonal-planar geometry and was coordinated to two nitrogen atoms and one carbon. Insertion of the small B(III) ion into the meso-fused phlorin analogue resulted in transforming the nonaromatic phlorin analogue to an aromatic B(III) benzitriphyrin(2.1.1) complex. Spectral and electrochemical studies supported the aromatic nature of the B(III) complex of benzitriphyrin(2.1.1). Theoretical studies supported the major contribution of the 18π delocalization pathway toward the aromatic nature of the B(III) meso-fused benzitriphyrin(2.1.1) in comparison to the 22π delocalization pathway. The B(III) benzitriphyrin(2.1.1) complex acts as a specific colorimetric and fluorogenic F-/CN- ion sensor.

Synthesis and Studies of Stable Nonaromatic Dithia Pyribenzihexaphyrins.

We report here one of the rare examples of expanded hexaphyrins named as dithia pyribenzihexaphyrin macrocycles containing six-membered rings such as pyridine and p-phenylene along with five-membered heterocycles such as pyrrole and thiophene as a part of a macrocyclic frame. Trifluoroacetic acid catalyzed [3 + 3] condensation of equimolar mixture of [10,10'-bis(p-tert-butyl phenyl)hydroxymethyl]-1,3-bis(2-thienyl)pyridine diol (2,6-pyri diol) and 1,4-bis(phenyl(1H-pyrrol-2-yl)methyl)benzene (p-benzidipyrrane) in CH2Cl2 followed by oxidation with DDQ afforded stable nonaromatic dithia 2,6-pyri-para-benzihexapyrins 1 and 2 in 6-8% yields. The macrocycles were characterized by high-resolution mass spectroscopy and 1D and 2D NMR spectroscopy. NMR studies revealed the nonaromatic nature of dithia 2,6-pyri-p-benzihexaphyrins and indicated that the para-phenylene ring prefers to be in quininoid form rather than in benzenoid form. The macrocycles displayed sharp absorption bands in the region of ∼380-500 nm and a broad band at ∼700 nm, reflecting their nonaromatic nature. Upon protonation, these macrocycles showed NIR absorption properties. The redox studies of macrocycles indicated their electron-deficient nature. The DFT/TD-DFT studies are in line with the experimental observations.

Synthesis and Properties of Dibenzothiophene Embedded Heteroporphyrins.

A series of new stable dibenzothiophene embedded heteroporphyrins were synthesized in 6-7% yields by condensing 1 equiv of dibenzothiophene-based tripyrrane with 1 equiv of four different diols, 2,5-bis(hydroxymethyl)heterocycles (furan, thiophene, selenophene, and tellurophene), under mild acid-catalyzed conditions in CH2Cl2. The formation of dibenzothiophene embedded heteroporphyrins was confirmed by high-resolution mass spectrometry and thoroughly characterized by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, absorption, electrochemical, and density functional theory/time-dependent density functional theory (DFT/TD-DFT) studies. The NMR studies indicated that the macrocycles were nonaromatic in nature. The electronic properties of the macrocycles were significantly altered as the heterocycle of the macrocycles was varied from furan to thiophene, selenophene, and tellurophene, as reflected clearly in the spectral and electrochemical properties. The macrocycles exhibited a sharp band in the region of 420-440 nm and a relatively broad absorption band(s) in the higher wavelength region of 550-800 nm. The oxa analogue was considerably blue-shifted as compared to the other macrocycles, whereas the tellura analogue exhibited relatively broadened and red-shifted absorption bands. Upon protonation of these macrocycles, the resulting diprotonated species displayed bathochromically shifted absorption bands, which were extended to the NIR region. DFT studies revealed that the macrocycles were highly distorted and strained and exhibited half chair conformation with restricted π-conjugation and confirmed their nonaromatic nature due to the lack of planarity of the macrocycle. TD-DFT studies were in agreement with the experimental spectral and electrochemical results.

Dibenzofuran/Dibenzothiophene-Embedded Dithia-bis(calix)-sapphyrins.

A series of first examples of dibenzofuran (DBF)/dibenzothiophene (DBT)-embedded dithia-bis(calix)-sapphyrins were synthesized by condensing 1 equiv of dibenzofuran/dibenzothiophene-based tripyrrane with 1 equiv of [2,2'-bithiophene]-5,5'-diylbis(aryl)methanol under mild acid-catalyzed conditions in CH2Cl2 followed by oxidation with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) and alumina column chromatographic purification afforded new dithia-bis(calix)-sapphyrins with two meso-sp3 carbons in 5-7% yields. The DBF/DBT-embedded dithia-bis(calix)-sapphyrins were characterized by HRMS (high-resolution mass spectrometry), 1H and 13C NMR, 1H-1H COSY, 1H-1H NOESY, 1H-13C HSQC, and 1H-13C HMBC spectroscopy, absorption spectroscopy, cyclic voltammetry, and density functional theory (DFT) studies. The macrocycles showed one broad absorption band at ∼553 nm with a shoulder peak at the higher energy side along with a sharp intense band at ∼415 nm. However, the protonated dithia-bis(calix)-sapphyrins showed large bathochromic shifts in the absorption bands, indicating that the electronic properties of dithia-bis(calix)-sapphyrins were altered significantly upon protonation of dithia-bis(calix)-sapphyrins. The electrochemical study indicated that dithia-bis(calix)-sapphyrins are relatively easier to reduce but difficult to oxidize. The DFT studies revealed that macrocycles adopt a highly folded half-chair conformation due to the disruption of conjugation of the macrocycle because of the presence of two sp3 meso-carbons. The DFT studies also support the significant bathochromic shifts observed for protonated dithia-bis(calix)-sapphyrins macrocycles.

Meso-Fused Carbatriphyrins(2.1.1) and Its Organo Phosphorus(V) Complex.

The first examples of phlorin analogues of meso-fused carbatriphyrins(2.1.1) and organo P(V) complex of one of the meso-fused carbatriphyrins were obtained by adopting a premodification strategy starting with fluorene as a fused polyaromatic precursor over a sequence of steps. The meso-fused carbatriphyrins(2.1.1) were obtained as their nonaromatic phlorin analogues owing to the unstable nature of the fully conjugated meso-fused carbatriphyrins(2.1.1). The organo P(V) complex of one of the meso-fused carbatriphyrins was prepared by treating the phlorin analogue of carbatriphyrin(2.1.1) with PCl3 in toluene/triethylamine at reflux for 1 h. The P(V) complex of the meso-fused carbatriphyrin(2.1.1) was found to be moderately aromatic and the resulting global conjugation pathways in the P(V) complex significantly alters the aromaticity of the fluorene unit. The nonaromatic nature of the phlorin analogues of the meso-fused carbatriphyrin(2.1.1) and the moderately aromatic nature of its P(V) complex were supported by X-ray crystallography, absorption spectroscopy, NMR studies together with nucleus-independent chemical shifts, anisotropy-induced current density, and harmonic oscillation stabilization energy calculations.