uu.seUppsala University Publications
Change search
ReferencesLink to record
Permanent link

Direct link
Preferential Solvation of a Highly Medium Responsive Pentacyanoferrate(II) Complex in Binary Solvent Mixtures: Understanding the Role of Dielectric Enrichment and the Specificity of Solute-Solvent Interactions
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
2016 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 120, no 35, 9422-9433 p.Article in journal (Refereed) Published
Abstract [en]

In this work, the preferential solvation of an intensely, solvatochromic ferrocyanide(II) dye involving a 4,4'-bipyridine-based ligand was examined in various binary solvent mixtures. Its solvatochromic behavior was rationalized in terms of specific and nonspecific solute-solvent interactions. An exceptional case of solvatochromic inversion was observed when going from alcohol/water to amide/water mixtures. These effects were quantified using Onsager's solvent polarity function. Furthermore, the sensitivity of the solvatochromism of the dye was determined using various solvatochromic parameters such as pi* expressing the dipolarity/polarizability of solvents and alpha expressing the hydrogen-bond-donor acidity of solvents. This analysis was useful for the rationalization of the selective solvation phenomena occurring in the three types of alcohol/water and amide/water mixtures studied. Furthermore, two preferential solvation models were employed for the interpretation of the experimental spectral results in binary solvent mixtures, namely, the model of Suppan on dielectric enrichment [J. Chem. Soc. Faraday Trans. 1 1987, 83, 495-509] and the model of Bosch, Roses, and co-workers [J. Chem. Soc., Perkin Trans. 2, 1995, 8, 1607-1615]. The first model successfully predicted the charge transfer energies of the dye in formamide/water and N-methylformamide/water mixtures, but in the case of MeOH/water mixtures, the prediction was less accurate because of the significant contribution of specific solute-solvent interactions in that case. The second model gave more insights for both specific solute-solvent as well as solvent- solvent interactions in the cybotactic region. The role of dielectric enrichment and specific interactions was discussed based on the findings.

Place, publisher, year, edition, pages
2016. Vol. 120, no 35, 9422-9433 p.
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-305469DOI: 10.1021/acs.jpcb.6b05868ISI: 000383005200016PubMedID: 27525362OAI: oai:DiVA.org:uu-305469DiVA: diva2:1038553
Available from: 2016-10-19 Created: 2016-10-18 Last updated: 2016-10-19Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
Papadakis, Raffaello
By organisation
Molecular Biomimetics
In the same journal
Journal of Physical Chemistry B
Physical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

Altmetric score

Total: 58 hits
ReferencesLink to record
Permanent link

Direct link