The first examples of stable phlorin analogues of dithiacorrphycene were synthesized by treating appropriate tetrapyrranes with two equivalents of trifluoroacetic acid in CH₂Cl₂ 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‐sp³‐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 Fe³⁺ ions by converting phlorin analogues of dithiacorrphycenes into dithiacorrphycene.

中文翻译：

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双硫杂卟啉四氢卟酚类似物的合成及其作为Fe3 +离子的特定化学计量传感器的应用

通过在CH ₂ Cl ₂中用两当量的三氟乙酸处理适当的四吡喃，然后用对氯苯酚氧化，合成了双硫杂蒽的稳定的phlorin类似物的第一个实例。四吡喃的氧化偶联导致形成了两个出乎意料的双硫藻卟啉类似物phlorin类似物，在meso- sp ^3时彼此不同碳，这两个大环很容易通过柱色谱法分离和分离。新的大环化合物已通过X射线晶体学确认，并通过HRMS，1D和2D NMR光谱，吸收光谱，循环伏安法和随时间变化的DFT研究进行了表征。X射线结构分析揭示了大环的高度紧张和扭曲的性质。大环显示出在一个不明确的吸收带λ ≈315nm和一个宽带λ ≈530纳米。由于两个大环均具有两个噻吩和两个带有一个可电离的内部NH的吡咯环，因此已研究了双硫杂卟啉类配基的类似物的阳离子传感特性。二硫杂藻的phlorin类似物可作为Fe ^3+的特定化学计量传感器 通过将双硫杂藻的phlorin类似物转化为双硫杂草环而产生离子。