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Stable Nonaromatic [20]Dithiaporphyrin (2.1.1.1) Macrocycles: Synthesis, Structure, Spectral, Electrochemical, and Metal Ion Sensing Studies

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Title Stable Nonaromatic [20]Dithiaporphyrin (2.1.1.1) Macrocycles: Synthesis, Structure, Spectral, Electrochemical, and Metal Ion Sensing Studies
 
Creator GANAPATHI, E
LEE, WZ
RAVIKANTH, M
 
Subject EXPANDED PORPHYRINS
TETRAPYRROLIC MACROCYCLES
MOBIUS AROMATICITY
BUILDING-BLOCK
HOMOPORPHYRINS
CYCLOPOLYPYRROLES
CHEMISTRY
 
Description 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.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-12-29T05:46:57Z
2014-12-29T05:46:57Z
2014
 
Type Article
 
Identifier JOURNAL OF ORGANIC CHEMISTRY, 79(20)9603-9612
0022-3263
http://dx.doi.org/10.1021/jo501724d
http://dspace.library.iitb.ac.in/jspui/handle/100/17230
 
Language English