Stable Nonaromatic [20]Dithiaporphyrin (2.1.1.1) Macrocycles: Synthesis, Structure, Spectral, Electrochemical, and Metal Ion Sensing Studies
| Autor: | Way Zen Lee, Emandi Ganapathi, Mangalampalli Ravikanth |
|---|---|
| Rok vydání: | 2014 |
| Předmět: |
Tetrapyrrolic Macrocycles
Building-Block Absorption spectroscopy Organic Chemistry Electrochemistry Photochemistry Porphyrin Homoporphyrins Metal Chemistry Crystallography chemistry.chemical_compound chemistry visual_art visual_art.visual_art_medium Thiophene Cyclopolypyrroles Moiety Expanded Porphyrins Spectroscopy Two-dimensional nuclear magnetic resonance spectroscopy Mobius Aromaticity |
| Zdroj: | The Journal of Organic Chemistry. 79:9603-9612 |
| ISSN: | 1520-6904 0022-3263 |
| Popis: | Stable nonaromatic [20] dithiaporphyrin (2.1.1.1) macrocycles were synthesized in decent yields by condensing readily available butene-2,3-diyl-bisthiophene-2,5diyl-bis(p-methoxyphenylmethanol) with different meso-aryl dipyrromethanes under mild acid catalyzed conditions. The [20]clithiaporphyrin (2.1.1.1) macrocydes are the first members of the expanded poiphyrin analogues of [18]dithiaporphyrin (1.1.1.1) and consist of two pyrroles and two thiophenes connected through five meso-carbon bridges. The [20]dithiaporphyrin macrocycles were confirmed by mass spectroscopy, 1D and 2D NMR spectroscopy, and X-ray crystallography. The X-ray structure revealed that the macrocycle is highly distorted and that the two thiophene rings are completely out from the "mean-plane" defined by the dipyrromethene moiety and the two meso-carbons. In the absorption spectrum, the macrocycles showed one strong band at similar to 420 nm and one weak band at similar to 720 nm. The electrochemical studies revealed that the macrocycles are stable under redox conditions. The metal sensing studies indicated that these macrocycles have the potential to sense specific metal ions such as Hg2+ ions. Two covalently linked dithiahomoporphyrin fluorophore dyads were synthesized by coupling iodo-functionalized dithiahomoporphyrin with an ethynyl-functionalized fluorophore such as boron dipyrromethene (BODIPY) and BF2 smaragdyrin under mild Pd(0) coupling conditions. The potential of these dyads as a fluorescent sensor for Hg2+ was explored, and the studies indicated that both dyads can be used as fluorescent sensors. |
| Databáze: | OpenAIRE |
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