Synthesis of Phlorin Analogues of Dithiacorrphycene and Their Use as Specific Chemodosimetric Sensors for Fe³⁺ Ions

Abstract

The first examples of stable phlorin analogues of dithiacorrphycene were synthesized by treating appropriate tetrapyrranes with two equivalents of trifluoroacetic acid in CH Cl followed by oxidation with p-chloranil. The oxidative coupling of tetrapyrrane resulted in the formation of two unexpected phlorin analogues of dithiacorrphycenes that differed from each other at the meso-sp -carbon, and the two macrocycles were easily separated and isolated by column chromatography. The novel macrocycles were confirmed by X-ray crystallography and characterized by HRMS, 1D and 2D NMR spectroscopy, absorption spectroscopy, cyclic voltammetry, and time-dependent DFT studies. X-ray structure analysis revealed the highly strained and distorted nature of the macrocycles. The macrocycles showed one ill-defined absorption band at λ≈315 nm and a broad band at λ≈530 nm. Because both macrocycles possess two thiophene and two pyrrole rings with one ionizable inner NH, the cation-sensing properties of the phlorin analogues of dithiacorrphycenes have been investigated. The phlorin analogues of dithiacorrphycenes act as specific chemodosimetric sensors for Fe ions by converting phlorin analogues of dithiacorrphycenes into dithiacorrphycene.

Synthesis of ABC‐Type 22‐Oxacorroles Bearing Three Different Five‐Membered Heterocycles at the meso Positions

“…Computational Details: All the computations for the compounds 2 – 5 were performed using of the Gaussian 09 program package as described previously …”

“…Computational Details: All the computations for the compounds 2-5 were performed using of the Gaussian 09 program package [22] as described previously. [23] Compound 7: In a three-necked 250 mL round-bottom flask, the furan mono-ol 6 (2 mL, 23.14 mmol) in diethyl ether (30 mL) was treated with nBuLi (36 mL, 57.85 mmol, 1.6 M solution in n-hexane) in the presence of TMEDA (8.7 mL, 57.85 mmol) under inert atmosphere at 0°C for 1 h. Thiophene 2-carbaldehyde (6.8 mL, 57.85 mmol) was added slowly to the reaction mixture and the reaction was stirred at 0°C for additional 1 h. After standard workup, the crude compound was subjected to silica gel column chromatography (60:40 pet ether ethyl acetate v/v) to afford the furan-diol 7 as a yellow semi-solid in 45 % yield (2.1 g). 1…”

Covalently Linked meso‐BODIPYnyl Dithiahomoporphyrins: Synthesis and Properties

“…[16] Synthesis of Diol (6): The required diol, 6 as E/Z mixture was synthesized by following our previously reported procedure. [7] Synthesis of BODPYs (8-10): Synthesis of the required BODIPY precursors (8-10) were achieved using reported procedures. [7] Synthesis of BODPYs (8-10): Synthesis of the required BODIPY precursors (8-10) were achieved using reported procedures.…”

“…[5] Synthesis of Tetrapyrrane 7: The required tripyrrane, 7 as E/Z mixture (pale yellow semi solid) was synthesized from diol 6 and excess pyrrole by following our previously reported procedure. [7] Synthesis of BODPYs (8-10): Synthesis of the required BODIPY precursors (8-10) were achieved using reported procedures. [8][9][10][11] The spectroscopic data is in good agreement with the reported data for the BODIPY precursors (8)(9)(10).…”

“…The required diol 6 (E/Z mixture) [5] and tetrapyrrane 7 (E/Z mixture) [7] were synthesized over sequence of steps by following our reported procedures. Different formyl-BODIPY precursors (8)(9)(10)(11) and -dipyrromethanyl aza-BODIPY (12) were synthesized by following the reported protocols.…”