Submitted by:

Neo, Meryday (S# 20)

Advanced Inorganic Chemistry, 14 September 2017
Journal Article:
N.M. Shishlov and S.L. Khursan
Effect of ion interactions on the IR spectrum of Benzenesulfonate ion.
Restoration of sulfonate ion symmetry in Sodium Benzene sulfonate ion dimer
Journal of Molecular Structure, 1123 (2016) 360-366

I. Introduction

The effect of interactions of cations on the IR spectrum in benzenesulfonate (BS) ion was studied
by Shishlov and Khursan (2016) by means of the density functional theory (Peica, 2006) as ionomers
(Benson, 2010) and polyelectrolytes, particularly the sulfonate ions, exhibit extensively flexible modes of
coordination and highly stable structure (Abdelhak, Amami, Hlil, Zi, & Cherni, 2015).

II. Summary

In this paper, Shishlov and Khursan based their hypothesis on Zundels research that for metal
cations, the only coordination probable with sulfonate ions is monodentate. The quantum chemical
computations were performed through Gaussian-09 software package and ChemCraft program was utilized
for visualization of results. To fully optimized the geometric factors as well as spectral vibration analysis,
B3LYP technique of the DFT was employed and 6-311G(d,p) was used as basis set. The nonexistence of
negative components in the diagonal slanted Hessian Matrix were the basis to conform the minima of the
potential energy surface. The researchers observed that at optimized conditions, contrary to Zundels
hypothesis, two structures are possible for BS-Na, bidentate and tridentate, but the formation of the former
is more favored in terms of enthalpy and Gibbs free energy than the latter. Further, they also found out that
the asymmetrical S-O bond lengths of benzenesulfonate due to the benzene ring, becomes symmetrical due
to the combined effects of the monodentate and bidentate coordinated sodium cations which exist
instantaneously in the dimer BS-Na. Thus, there was a partial restoration of the C3v point group for the
model salt BS-Na as the S-O bond became almost the same in length.

III. Conclusion

The results of this study are somewhat consistent with the findings from the study performed by
Lu et al. that the metal cation-sulfonate interface seemed to lock the binding portion in their desired
structure to a high extent, so that compared to non-sulfonated copolymers there are reasonably minute
variations in the relative intensities of conformation-sensitive bands (Lu, Runt, & Painter, 2009). In
addition, based on the study conducted by Doan on categorizing sulfonate vibrational modes, the metal ions
change the sulfonate exchange location at all conditions of hydration, adhering to the area with C3V
symmetry and a high orbital overlapping property with sulfonate sulfur and atoms of oxygen were observed,
thus retaining the C3v point group (Doan, 2017). The computation results stating that an intense vibration
occurs in the specified absorption bands for BS-Na however, contradicts the result in IR spectra which
showed rather low intensity. Nonetheless, compared to other alkali metals, such as Li, K and Ce, the
researchers concluded that Na coordination with the sulfonate ion showed that the S-O vibrations were less
asymmetric than isolated ion pair of BS. This experimental observation can be used as baseline data in
predicting the coordination behavior of other monovalent cations. The dilemma for assigning absorption
bands (ABs) for S-O stretching vibrations still remained unresolved, nevertheless, the authors were able to
establish that BS environment affects the absorption bands positions. It is suggested therefore, that further
studies need to be conducted to analyze other ABs positions to come up to a more conclusive results.
IV. References

1. Abdelhak, J., Amami, M., Hlil, E., Zi, M., & Cherni, S. N. (2015). Studies on Cobalt(II) Complexes
with Benzenesulfonate: Synthesis, Crystal Structure, and Spectroscopic and Magnetic Properties.
Journal of Superconductivity, 1-10 doi:10.1007/s10948-015-3268-2.
2. Benson, S. D. (2010). The Effect of Nanoscale Particles and Ionomer Architecture on the
Crystallization Behavior of Sulfonated Syndiotactic Polystyrene. Retreived September 3, 2017,
from
https://theses.lib.vt.edu/theses/available/etd02062011171639/unrestricted/Benson_SonyaD_D_20
11_4.pdf.
3. Doan, J. H. (2017). Categorization of sulfonated ionomer vibrational modes by exchange site
symmetry. Retreived September 3,2017, from
https://repository.library.northeastern.edu/files/neu:cj82q383k/fulltext.pdf.
4. Lu, M., Runt, J., & Painter, P. (2009). An Infrared Spectrocopic Study of a Polyester Copolymer
Ionomer Based on Poly(ethylene oxide). Macromolecules, 42, 65816587, doi:
10.1021/ma900978d.
5. Peica, N. (2006). Vibrational spectroscopy and density functional theory calculations on biological
molecules. Retreived Sepetember 3, 2017, from http://d-nb.info/982932146/34.