Rational Synthesis of Highly Stable Dithienopyrrole-Embedded BODIPYs Exhibiting Large Stokes Shift.

A series of dithienopyrrole (DTP) embedded BODIPYs were synthesized and structurally characterized. These BODIPYs have strong absorption in the green region and broad emission in the red region with a large Stokes shift ranging from 3100 to 4200 cm. Interestingly, all three BODIPYs show intramolecular charge transfer interaction (ICT).

Access to Isoxazoles via Photo-oxygenation of Furan Tethered α-Azidoketones.

Photocatalyst-free visible light-enabled direct oxygenation of furan-tethered α-azidoketones was studied. The reaction yielded various products depending on the substituents, with isoxazoles forming as the major products. The findings suggest that singlet oxygen was generated during the reaction and reacted with α-azidoketones in a [4 + 2] fashion to yield endoperoxides, which rearranged in multiple ways to generate isoxazoles.

Carbazole-embedded -benziporphyrinoid: synthesis, structure and a reversible chemodosimeter for mercury(II) ions.

The first carbazole-embedded -benziporphyrinoid is synthesized by a [3+1] acid-catalyzed condensation between appropriate coupling partners. The macrocycle 1 exhibited orange emission and showed a large Stokes shift of 5831 cm. Intriguingly, it shows a selective affinity towards Hg ions over other metal-ions in a reversible manner.

Template Assisted Formation of 32 and 34π Octaphyrins Embedded with Dithienopyrrole Cores: A New Scaffold to Unravel Proton Coupled Redox Switching and (Anti)Aromaticity.

Herein, we report two distinct octaphyrins obtained by the condensation of new dithieno[3,2-b:2',3'-d]pyrrole based tetrapyrrane under two different acidic conditions. Fourfold meso-substituted octaphyrin was the major product when the reaction was performed in the presence of an aryl aldehyde using trifluoroacetic acid. Whereas, the sixfold meso-substituted octaphyrin was obtained when the precursor was condensed with pentafluorobenzaldehyde using para-toluenesulfonic acid.

Stable Inner 2H Tautomer of N-Confused-like Porphyrin Embedded with a Carbazole Subunit: Synthesis, Metal Coordination, and Magnetic and Anion Sensing Studies.

A new class of N-confused porphyrin embedded with a carbazole subunit was prepared via [3 + 1] acid-catalyzed condensation of appropriate precursors. underwent smooth metal complexation with Pd(II) and Cu(II) salts to provide the corresponding diamagnetic and paramagnetic , respectively. The single-crystal X-ray structure of is evident with a square-planar Pd-center through C-H activation of inverted pyrrole.

Conformationally Locked Cyclo[2]Dipyrrins Linked with Anthracene Subunits: Synthesis and Chiroptical Properties.

Herein, we report the synthesis of anthracene-containing twisted cyclo[2]dipyrrin 1 by utilizing a non-planar building block, 1,5-dipyrrylanthracene (1,5-DPA). The non-planar nature of the macrocycle enhanced the solubility and helped in structural characterization. Macrocycle 1 adopts a twisted 'figure of eight' conformation stabilized by strong intramolecular H-bonding interactions and exists as a pair of helical enantiomers, as revealed by X-ray crystallographic analysis.

Synthetic Model for FRET Constructed from Covalently Linked Porphyrin Dimers through a Pyrene Bridge.

We report the synthesis and characterization of two porphyrin arrays CF-PyZnDP and Mes-PyZnDP covalently linked by a pyrene moiety which differs from their substituents at their -positions. The key precursor bis-dipyrromethane linked with a pyrene bridge was prepared by the acid-catalyzed condensation of pyrene-1,6-dialdehyde with excess pyrrole. The synthesis of CF-PyZnDP was carried out via two different synthetic routes, with one being efficient over the other.

Synthesis, Structure, and Optical Properties of a Bis-Macrocycle Derived from a Highly Emissive 1,3,6,8-Tetra(1-pyrrol-2-yl)pyrene.

A tetra-functionalized pyrene precursor is prepared using the Suzuki-Miyaura coupling of 1,3,6,8-tetrabromopyrene with -Boc-2-pyrroleboronic acid. displayed a blue emission with a high quantum yield (ϕ = 0.89).

Conformationally Distinct [26]Heterorubyrin(1.1.0.1.1.0) Macrocycles and Their Bis-BODIPYs: Synthesis, Structure, and Optical Properties.

Two conformationally different [26]rubyrin(1.1.0.

Disruption of Antiaromaticity in Structurally Related Expanded Porphyrin-like Macrocycles with Benzene Linkers.

1,4-Phenylene-linked cyclotrimer () and cyclotetramer () have been synthesized via Lewis acid-catalyzed self-condensation of appropriate precursors. Structural and Density Functional Theory (DFT) studies reveal the disruption of annulenic conjugation in both and by linking phenylene rings prevented them from global antiaromaticity. The single crystal X-ray structure of reveals all the nitrogens are pointing toward the macrocyclic core with near-planar and square-shaped geometry, thus in sharp contrast to the ring-strained conformation of .

Planar hexaphyrin-like macrocycles turning into bis-BODIPYs with box-shaped structures exhibiting excitonic coupling.

Planar carbazole based hexaphyrin-like macrocycles with bis-coordinating cores and box-shaped cyclic BODIPYs were synthesized. Solution and solid-state structure analysis of the free macrocycles indicates an inversion of two pyrrole rings, resulting in a two-dipyrrin-like environment. The BF complexes show large Stokes shifts and exhibit excitonic coupling, fine-tuned by the -substituents.

Double intramolecular hydrogen transfer assisted dual emission in a carbazole-embedded porphyrin-like macrocycle.

The introduction of a pyrrole ring at one of the meso positions of carbazole-based porphyrins lowers the structural symmetry and results in dual emission, which strongly depends on the excitation wavelength and temperature. The origin of dual emission induced by NH-tautomerism is confirmed via photophysical and DFT calculations.

DMSO as a Methine Source in TFA-Mediated One-Pot Tandem Regioselective Synthesis of 3-Substituted-1-Aryl-1-Pyrazolo-[3,4-]quinolines from Anilines and Pyrazolones.

An acid-mediated and DMSO participant one-pot tandem synthesis of 3-substituted-1-aryl-1-pyrazolo-[3,4- ]quinoline from readily available anilines and pyrazolones was achieved. This method enables regioselective construction of the valuable heterocycles under transition-metal and oxidant-free conditions in which DMSO acts as a methine source as well as solvent making this process an environmentally benign approach. A broad range of diversely substituted aryl amines and pyrazolines are successfully employed in this reaction to access a series of pyrazolo[4,3-]quinolones through a novel cascade mechanism.

Carbazole-Based Porphyrins: Synthesis, Structure-Photophysical Property Correlations, and Mercury Ion Sensing.

The synthesis of a new class of carbazole based macrocycles via [3 + 1] acid-catalyzed condensation is reported. Spectroscopic investigations and computational studies imply that these macrocycles have a large influence on the electronic structure in comparison to previously reported carbazole based macrocycles. Macrocycle bearing a furan ring reversibly binds aqueous Hg with high affinity over other M ions.

Synthesis, Structure, and Optical Properties of Di--benzihexaphyrins (1.1.0.0.0.0) and Di--benziheptaphyrins (1.0.1.0.0.0.0): Blackening of -Phenylene-Linked Dicarbaporphyrinoids by Simple π-Expansion.

Acid-catalyzed condensation of a newly prepared di--benzipentapyrrane with appropriate mono- and diheterocyclic dialcohols selectively produced stable di--benzihexaphyrins and di--benziheptaphyrins with only two -carbon bridges. Single-crystal X-ray diffraction analyses reveal planar conformation with slight distortion of bridged phenylene rings. Despite the presence of -phenylene units interrupting the global delocalization, the presence of bithiophene units in di--benziheptaphyrins exhibits altered optical features covering the entire visible region (ca.

Synthesis of a Black Dye with Absorption Capabilities Across the Visible-to-Near-Infrared Region: A MO-Mixing Approach via Heterometal Coordination of Expanded Porphyrinoid.

An expanded metalloporphyrin-based "black dye" Au-Pd oxohexaphyrin () with absorption capabilities across the visible-to-near-infrared (NIR) range was synthesized. This black dye, , possessed efficient light-harvesting and photostable capabilities, which were indicative of superior photothermal (PT) conversion abilities. Encapsulation of with a micellar nanocapsule resulted in a compound that demonstrated intense photoacoustic (PA) properties in the NIR region in water.

Planar Antiaromatic Core-Modified 24π Hexaphyrin(1.0.1.0.1.0) and 32π Octaphyrin(1.0.1.0.1.0.1.0) Bearing Alternate Hybrid Diheterole Units.

The Lewis acid catalyzed self-condensation of hybrid diheterole (furan-pyrrole and thiophene-pyrrole) precursors has afforded novel Hückel antiaromatic 24π hexaphyrin(1.0.1.

Visible-Light Driven Photocascade Catalysis: Union of N,N-Dimethylanilines and α-Azidochalcones in Flow Microreactors.

N,N-Dimethylanilines were coupled with α-azidochalcones using visible-light driven Ru(bpy)(PF) catalyzed photocascade continuous flow microfluidic approach that involves the creation of one C-C and two C-N new bonds. The reaction involves dual photocatalysis ensuing two sp C-H bond functionalization of N,N-dimethylanilines. To explore the scope of the reaction, 20 different 1,3-diazabicyclo[3.

Synthesis, structure and photophysical properties of ferrocenyl or mixed sandwich cobaltocenyl ester linked meso-tetratolylporphyrin dyads.

We report here the design and synthesis of porphyrin-metallocene dyads consisting of a metallocene [either ferrocene or mixed sandwich η(5)-[C5H4(COOH)]Co(η(4)-C4Ph4) connected via an ester linkage at meso phenyl position of either free-base or zinc porphyrin. All these dyad systems were characterized by various spectroscopic and electrochemical methods. A dimeric form of this molecule was observed in the X-ray crystal structure of Zn-TTPCo.

Confusion of Möbius aromaticity: disruption of annulenic pathway in singly N-confused [28]hexaphyrin and its mono-Pd(II) complex.

Singly N-confused [26] and [28]hexaphyrins (4, 5) with planar and twisted structures, respectively, were prepared via the acid catalyzed [3 + 3] condensation of N-confused and regular tripyrrane precursors. Hückel aromaticity is observed for [26]hexaphyrin, while the [28]hexaphyrin and its mono-Pd(II) complex exhibit "nonaromaticity" in spite of their Möbius-type structures, judging from the spectroscopic features and theoretical calculations.

Synthesis and reactivity of 5,10,15-triaryl doubly N-confused bilanes.

A series of 5,10,15-tris(pentafluorophenyl) doubly N-confused bilanes were synthesized in a stepwise manner with the aid of sterically demanding N-protecting groups, in which the difference in reactivity between regular pyrrole and N-confused pyrrole plays a crucial role in the synthetic strategy. Some doubly N-confused bilanes were converted into porphyrinoids or a unique 2:2 copper(II) complex with a helical structure. In addition, the conformations and electronic states of the doubly N-confused bilanes were investigated theoretically, giving fruitful information about the effect of confusion on the bilane skeleton.