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A DFT study of pyrrole-isoxazole derivatives as chemosensors for fluoride anion.

Jin R, Sun W, Tang S - Int J Mol Sci (2012)

Bottom Line: It turned out that the unique selectivity of AIC derivatives for F(-) is ascribed to their ability of deprotonating the host sensors.Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT).The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

View Article: PubMed Central - PubMed

Affiliation: College of Chemistry and Chemical Engineering, Chifeng University, Chifeng 024000, China; E-Mail: Cfxyhxx@163.com.

ABSTRACT
The interactions between chemosensors, 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC) derivatives, and different anions (F(-) Cl(-), Br(-), AcO(-), and H(2)PO(4) (-)) have been theoretically investigated using DFT approaches. It turned out that the unique selectivity of AIC derivatives for F(-) is ascribed to their ability of deprotonating the host sensors. Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT). The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

No MeSH data available.


Geometries of 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4- carboxamide (AIC) and its derivatives, along with atom numbering.
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f2-ijms-13-10986: Geometries of 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4- carboxamide (AIC) and its derivatives, along with atom numbering.

Mentions: Recently, a fluoride chemosensor made of a derivative of pyrrole-isoxazole, 3-amino-5-(4,5,6, 7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC, Scheme I), has been reported [21]. AIC shows both changes in its UV-vis absorption and fluorescence emission spectra upon the addition of F−, resulting in a higher selectivity for fluoride detection compared to other anions in CH3CN. Interactions of AIC with F− cause a red-shift in UV-vis absorption and a Stokes shift in fluorescence emission due to the deprotonation of the active pyrrole-NH moiety of AIC by F−. To the best of our knowledge, neither calculations of the host-guest interactions with the basis set superposition error (BSSE) corrections nor sophisticated level optimizations for the neutral, anion, and complexes forms of AIC derivatives in ground states (S0) and first excited singlet states (S1) have been reported so far.


A DFT study of pyrrole-isoxazole derivatives as chemosensors for fluoride anion.

Jin R, Sun W, Tang S - Int J Mol Sci (2012)

Geometries of 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4- carboxamide (AIC) and its derivatives, along with atom numbering.
© Copyright Policy - open-access
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC3472725&req=5

f2-ijms-13-10986: Geometries of 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4- carboxamide (AIC) and its derivatives, along with atom numbering.
Mentions: Recently, a fluoride chemosensor made of a derivative of pyrrole-isoxazole, 3-amino-5-(4,5,6, 7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC, Scheme I), has been reported [21]. AIC shows both changes in its UV-vis absorption and fluorescence emission spectra upon the addition of F−, resulting in a higher selectivity for fluoride detection compared to other anions in CH3CN. Interactions of AIC with F− cause a red-shift in UV-vis absorption and a Stokes shift in fluorescence emission due to the deprotonation of the active pyrrole-NH moiety of AIC by F−. To the best of our knowledge, neither calculations of the host-guest interactions with the basis set superposition error (BSSE) corrections nor sophisticated level optimizations for the neutral, anion, and complexes forms of AIC derivatives in ground states (S0) and first excited singlet states (S1) have been reported so far.

Bottom Line: It turned out that the unique selectivity of AIC derivatives for F(-) is ascribed to their ability of deprotonating the host sensors.Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT).The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

View Article: PubMed Central - PubMed

Affiliation: College of Chemistry and Chemical Engineering, Chifeng University, Chifeng 024000, China; E-Mail: Cfxyhxx@163.com.

ABSTRACT
The interactions between chemosensors, 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC) derivatives, and different anions (F(-) Cl(-), Br(-), AcO(-), and H(2)PO(4) (-)) have been theoretically investigated using DFT approaches. It turned out that the unique selectivity of AIC derivatives for F(-) is ascribed to their ability of deprotonating the host sensors. Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT). The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

No MeSH data available.