10.1021/jp404184x.s001
Natalia Piergies
Natalia
Piergies
Edyta Proniewicz
Edyta
Proniewicz
Yukihiro Ozaki
Yukihiro
Ozaki
Younkyoo Kim
Younkyoo
Kim
Leonard
M. Proniewicz
Leonard
M.
Proniewicz
Influence of Substituent Type and Position on the
Adsorption Mechanism of Phenylboronic Acids: Infrared, Raman, and
Surface-Enhanced Raman Spectroscopy Studies
American Chemical Society
2016
Raman
fluorophenylboronic
SERS
phenyl ring
phenylboronic acid isomers
formylphenylboronic
DFT
ground state geometry
B 3LYP method
2016-02-19 03:47:28
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Influence_of_Substituent_Type_and_Position_on_the_Adsorption_Mechanism_of_Phenylboronic_Acids_Infrared_Raman_and_Surface_Enhanced_Raman_Spectroscopy_Studies/2396827
This paper shows systematic spectroscopic
studies using Fourier-transform
infrared absorption (FT-IR), Fourier-transform Raman (FT-Raman), and
surface-enhanced Raman (SERS) in an aqueous silver sol of fluoro and
formyl analogues of phenylboronic acids: 2-fluorophenylboronic acid
(2<i>-</i>F-PhB(OH)<sub>2</sub>), 3-fluorophenylboronic
acid (3-F-PhB(OH)<sub>2</sub>), 4-fluorophenylboronic acid (4-F-PhB(OH)<sub>2</sub>), 2-formylphenylboronic acid (2-CHO-PhB(OH)<sub>2</sub>),
3-formylphenylboronic acid (3-CHO-PhB(OH)<sub>2</sub>), and 4-formylphenylboronic
acid (4-CHO-PhB(OH)<sub>2</sub>). To produce an extensive table of
vibrational spectra, density functional theory (DFT) calculations
with the B3LYP method at the 6-311++G(d,p) level of theory were performed
for the ground state geometry of the most stable species, dimers in <i>cis</i>–<i>trans</i> conformation. On the basis
of the SERS spectral profile, the adsorption modes of the phenylboronic
acid isomers were proposed. The type of substituent and its position
in the phenyl ring have a strong influence on the geometry of isomers
on the silver nanoparticle’s surface. This effect was especially
evident in the case of 4-CH-PhB(OH)<sub>2</sub>, for which dearomatization
of the phenyl ring took place upon adsorption.