Synthesis, spectroscopic and electrochemical investigation on the conformational features of meso-5-formylthien-2-ylporphyrins and its terpyridinylthien-2-ylporphyrin and Porphyrin-Corrole dyad

IF 2.1 3区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Journal of Sulfur Chemistry Pub Date : 2024-03-03 DOI:10.1080/17415993.2023.2279666

V. Vinoth Kumar , P. Gayathri , C. Arunamaheswari , P. Bhavana , R. Prasath

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Abstract

A facile approach for the syntheses of regioselective meso- mono, di (cis and trans), and tri formylthien-2-ylporphyrins from meso-tetrathien-2-ylporphyrin (ThP) is presented. The synthesized meso- mono formylthien-2-ylporphyrin ThP-CHO was further functionalized to 5-((5-terpyridinyl)thien-2-yl)-10,15,20-tris(thien-2-yl)porphyrin (ThP-TPy) and Porphyrin-Corrole (Por-Cor) dyad. The influence of formyl substitution and further functionalization on meso- thien-2-yl ring(s) with porphyrin central π-system is examined through UV–Vis absorption, ¹H NMR spectroscopy and electrochemical studies. The red shift of Soret band and Q bands in the absorption spectrum and the redox potentials are shown to be dependent on the number of substitution (ThP-CHO, 424 nm < ThPt-(CHO)₂ and ThPc-(CHO)₂, 425 nm < ThP(CHO)₃, 427 nm). The significant variation in redox potentials and distinct bathochromic shift in the absorption bands in the series of formyl derivatives, ThP-TPy and Por-Cor dyad have been explained based on the near-planar orientation of the meso-thienyl groups with the porphyrin core.

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介-5-甲酰基噻吩-2-基卟啉及其萜吡啶基噻吩-2-基卟啉和卟啉-科罗尔二元化合物构象特征的合成、光谱学和电化学研究

本文介绍了一种从中生四噻吩-2-基卟啉（ThP）合成具有区域选择性的中生一甲酰噻吩-2-基卟啉、二甲酰噻吩-2-基卟啉（顺式和反式）和三甲酰噻吩-2-基卟啉的简便方法。合成的中-单甲酰噻吩-2-基卟啉 ThP-CHO 被进一步官能化为 5-((5-叔吡啶基)噻吩-2-基)-10,15,20-三(噻吩-2-基)卟啉（ThP-TPy）和卟啉-科罗尔（Por-Cor）二元化合物。通过紫外-可见吸收、1H NMR 光谱和电化学研究，考察了甲酰基取代和进一步官能化对具有卟啉中心 π 系统的介-噻吩-2-基环的影响。结果表明，吸收光谱中索雷特带和 Q 带的红移以及氧化还原电位取决于取代的数量（ThP-CHO，424 nm <；ThPt-(CHO)2 和 ThPc-(CHO)2，425 nm <；ThP(CHO)3，427 nm）。甲酰基衍生物、ThP-TPy 和 Por-Cor 二聚体系列中氧化还原电位的显著变化和吸收带的明显浴色偏移是基于介噻吩基团与卟啉核心的近平面取向。

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来源期刊

Journal of Sulfur Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

4.10

自引率

9.10%

发文量

审稿时长

6-12 weeks

期刊介绍： The Journal of Sulfur Chemistry is an international journal for the dissemination of scientific results in the rapidly expanding realm of sulfur chemistry. The journal publishes high quality reviews, full papers and communications in the following areas: organic and inorganic chemistry, industrial chemistry, materials and polymer chemistry, biological chemistry and interdisciplinary studies directly related to sulfur science. Papers outlining theoretical, physical, mechanistic or synthetic studies pertaining to sulfur chemistry are welcome. Hence the target audience is made up of academic and industrial chemists with peripheral or focused interests in sulfur chemistry. Manuscripts that truly define the aims of the journal include, but are not limited to, those that offer: a) innovative use of sulfur reagents; b) new synthetic approaches to sulfur-containing biomolecules, materials or organic and organometallic compounds; c) theoretical and physical studies that facilitate the understanding of sulfur structure, bonding or reactivity; d) catalytic, selective, synthetically useful or noteworthy transformations of sulfur containing molecules; e) industrial applications of sulfur chemistry; f) unique sulfur atom or molecule involvement in interfacial phenomena; g) descriptions of solid phase or combinatorial methods involving sulfur containing substrates. Submissions pertaining to related atoms such as selenium and tellurium are also welcome. Articles offering routine heterocycle formation through established reactions of sulfur containing substrates are outside the scope of the journal.