Reversible redox-based optical sensing of parts per million levels of nitrosyl cation in organic solvents by osmium chromophore-based monolayers

Tarkeshwar Gupta, Revital Cohen, Guennadi Evmenenko, Pulak Dutta, Milko van der Boom

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Exposure of an osmium(II)-based monolayer on glass to organic solvents containing 0.36-116 ppm of NOBF4 results in one-electron transfer from the covalently immobilized complexes to the inorganic analyte with concurrent optical changes. The NO+ induced oxidation of the monolayer can be detected optically with an of-the-self-UV/vis spectrophotometer (260-800 nm). The redox-based NO+ detection and quantification system can be reset with water within ∼20 s for at least 40 times. The reaction of the monolayer with a THF solution containing 5 ppm of NOBF 4 follows pseudo first-order kinetics in the monolayer with ΔG‡298K = 21.5 ±0.7 kcal/mol, ΔH‡ = 9.5 ± 0.3 kcal/mol, and ΔS‡ = -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).

Original languageEnglish
Pages (from-to)4655-4660
Number of pages6
JournalJournal of Physical Chemistry C
Volume111
Issue number12
DOIs
Publication statusPublished - Mar 29 2007

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Osmium
osmium
Chromophores
Organic solvents
chromophores
Cations
Monolayers
Positive ions
cations
spectrophotometers
electron transfer
synchrotrons
density functional theory
reflectance
oxidation
glass
kinetics
Ultraviolet spectrophotometers
water
Synchrotrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Reversible redox-based optical sensing of parts per million levels of nitrosyl cation in organic solvents by osmium chromophore-based monolayers. / Gupta, Tarkeshwar; Cohen, Revital; Evmenenko, Guennadi; Dutta, Pulak; van der Boom, Milko.

In: Journal of Physical Chemistry C, Vol. 111, No. 12, 29.03.2007, p. 4655-4660.

Research output: Contribution to journalArticle

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AU - van der Boom, Milko

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