title: Surface-Enhanced Raman Spectroelectrochemistry of TTF-Modified Self-Assembled Monolayers.
abstract: Surface-enhanced Raman spectroscopy (SERS) was used to monitor the response of a self-assembled monolayer (SAM) of a tetrathiafulvalene (TTF) derivative on a gold film-over-nanosphere electrode. The electrochemical response observed was rationalized in terms of the interactions between TTF moieties as the oxidation state was changed. Electrochemical oxidation to form the monocation caused the absorbance of the TTF unit to coincide with both the laser excitation wavelength and the localized surface plasmon resonance (LSPR), resulting in surface-enhanced resonance Raman scattering (SERRS). The vibrational frequency changes that accompany electron transfer afford a high-contrast mechanism that can be used to determine the oxidation state of the TTF unit in an unambiguous manner.
authors: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors: Walter F
authors: WF
authors: Paxton
authors: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors: Samuel L
authors: SL
authors: Kleinman
authors: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors: Ashish N
authors: AN
authors: Basuray
authors: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors: J Fraser
authors: JF
authors: Stoddart
authors: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors: Richard P
authors: RP
authors: Van Duyne
keywords: LSPR; SAM; SERS; catenanes; rotaxanes; spectroelectrochemistry; tetrathiafulvalene