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Interaction between rhodanine and silver species on a nanocolloidal surface and in the solid state
Author(s) -
Marzec Katarzyna M.,
Gawel Bartlomiej,
Lasocha Wieslaw,
Proniewicz Leonard M.,
Malek Kamilla
Publication year - 2010
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2479
Subject(s) - tautomer , deprotonation , chemistry , raman spectroscopy , crystallography , molecule , rhodanine , lone pair , adsorption , ion , density functional theory , inorganic chemistry , stereochemistry , computational chemistry , organic chemistry , physics , optics
This paper discusses and compares molecular interactions of rhodanine (Rd), the heterocyclic compound containing N, S, and O atoms, with two forms of silver species, i.e. Ag(I) ions and silver nanocolloidal particles. Vibrational spectroscopic and powder crystallography studies on coordination of Ag(I) ions in the solid state, supported by density functional theory, clearly indicate complexation through the nitrogen (the deprotonated imino group) and exocyclic sulfur atoms. Molecules of the complex are arranged in a one‐dimensional infinite polymeric chain structure that intertwines to give a helix motif. On the other hand, adsorption geometry of Rd on the silver surface was determined by using surface‐enhancement Raman scattering (SERS) spectroscopy. Observed differences between the SERS and the normal Raman spectra of Rd suggest that Rd adsorbs on the silver species after the rearrangement of the keto‐thione form into the enol‐thiol tautomer in acidic and neutral solutions. This leads to adsorption on this silver species through the thiolate ion. On the other hand, the alkaline pH forces first N‐deprotonation of Rd, and, in consequence, the obtained anion of the keto‐thione form interacts with the silver surface as a result of the presence of lone pairs of nitrogen and sulfur atoms, similar to the case discussed for the solid state. Copyright © 2009 John Wiley & Sons, Ltd.