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Publication Type
Journal Article
UWI Author(s)
Author, Analytic
Bakir, Mohammed A ; Green, O. ; Gyles, C
Author Affiliation, Ana.
Department of Chemistry
Article Title
Molecular sensing behavior of the first Mn(I)-compound of di-2-pyridylketone-p-mitrophenylhydrazone (dpknph), fac-[Mn(CO)3-(dpknph)Br]
Medium Designator
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Connective Phrase
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Journal Title
Inorganica Chimica Acta
Translated Title
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Reprint Status
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Date of Publication
2005
Volume ID
358
Issue ID
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Page(s)
1835-1840
Language
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Connective Phrase
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Location/URL
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ISSN
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Notes
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Abstract
The reaction between [Mn(CO)5Br] and di-2-pyridylketone-p-nitrophenylhydrazone (dpknph) in diethyl ether under ultrasonic conditions gave fac-[Mn(CO)3(dpknph)Br] in good yield. Optical and thermodynamic measurements on fac-[Mn(CO)3(dpknph)Br] in non-aqueous polar solvents revealed reversible interconversion between two intense charge transfer absorption bands due to pp* (dpk), followed by dpk ? nitro intraligand charge transfer transition (ILCT), mixed with metal ligand charge transfer transition (MLCT) due to . In non-polar solvents, a single absorption band appeared. Extinction coefficients of 46 200 2000 and 28 400 2000 M-1 cm-1 were calculated in DMSO for the low- and high-energy electronic states of fac-[Mn(CO)3(dpknph)Br] using excess NaBF4. Changes in enthalpy (?H) of +14.0 and -12.1 kJ mol-1, entropy (?S) of +28.65 and -64.30 J mol-1 K-1, and free energy (?G) of +5.48 and +7.08 kJ mol-1 at 298 K were calculated for the interconversion between the high and low energy electronic states of fac-[Mn(CO)3(dpknph)Br]. These results allow for the use of these systems (fac-[Mn(CO)3(dpknph)Br] and surrounding solvent or solute molecules) as optical sensors for a variety of physical and chemical stimuli that include metal ions. Group 12 metal ions in concentrations as low as 1.00 10-9 M can be detected and determined using fac-[Mn(CO)3(dpknph)Br] in dmso in the presence and absence of NaBH4....
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Keywords
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