Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers
Exposure of an osmium(II)-based monolayer on glass to organic solvents containing 0.36-116 ppm of NOBF{sub 4} results in one-electron transfer from the covalently immobilized complexes to the inorganic analyte with concurrent optical changes. The NO{sup +} induced oxidation of the monolayer can be detected optically with an off-the-self-UV/vis spectrophotometer (260-800 nm). The redox-based NO{sup +} detection and quantification system can be reset with water within {approx}20 s for at least 40 times. The reaction of the monolayer with a THF solution containing 5 ppm of NOBF{sub 4} follows pseudo first-order kinetics in the monolayer with {Delta}G{sup {double_dagger}}{sub 298K} = 21.5 {+-} 0.7 kcal/mol, {Delta}H{sup {double_dagger}} = 9.5 {+-} 0.3 kcal/mol, and {Delta}S{sup {double_dagger}} = -40.6 {+-} 1.1 eu. The monolayer structure and properties have been resolved by electrochemical measurements and synchrotron X-ray reflectivity measurements in combination with density functional theory calculations (B3LYP/SDD level of theory).
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
- Sponsoring Organization:
- Doe - Office Of Science
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 930378
- Report Number(s):
- BNL-81100-2008-JA; TRN: US0901378
- Journal Information:
- Journal of Physical Chemistry C, Vol. 111; ISSN 1932-7447
- Country of Publication:
- United States
- Language:
- English
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