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Anion effect on the aggregation behavior of the long-chain spacers dicationic imidazolium-based ionic liquids

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Abstract

This work reports the study of the anion effect on the aggregation behavior of the long-chain spacers of dicationic imidazolium-based ionic liquids (ILs) in a 4.75 % (v/v) ethanol-water solution as well as in ethanol (95 %). The anions studied were Br−, NO3 −, BF4 −, SCN− and NTf2 −. Aggregation behavior was investigated by differential scanning calorimetry (DSC), conductivity, surface tension, and fluorescence. In the ethanol-water solution, the critical aggregation concentration (CAC), free energy aggregation (∆G°a), and the ionization degree (α) all significantly decreased with the increase in anion hydrophobicity. In ethanol, the CAC and ∆G°a values also decreased with the increase in anion size and hydrophobicity. The free energy adsorption (∆G°ads) data showed that the dicationic ILs have good surfactant activity, and this property improved with the decrease in the hydration radius of the anions. The anion volumes calculated also showed a good correlation with the CAC values for aggregation in ethanol-water solution and ethanol.

Favored aggregation of imidazolium based dicationic ILs by the increase in the anion hydrophobicity

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Acknowledgments

The authors acknowledge the financial support from the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)—Universal/Proc. 474895/2013-0 and Universal/Proc. 475556/2012-7, Coordenação de Aperfeiçoamento de Pessoal de Nivel Superior (CAPES) (Edital pró-equipamentos no. 01/2007), and the Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (FAPERGS)—Edital Pesquisador Gaúcho. The fellowships are from CNPq (M.A.P.M., C.R.B.) and CAPES (I.M.G., P.R.S.S.).

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Authors and Affiliations

  1. Núcleo de Química de Heterociclos (NUQUIMHE), Department of Chemistry, Federal University of Santa Maria, UFSM, CEP: 97105-900, Santa Maria, RS, Brazil

    Clarissa P. Frizzo, Caroline R. Bender, Paulo R. S. Salbego & Marcos A. P. Martins

  2. Biomaterials for Osseointegration and Novel Engineering (BONE) Lab, Department of Bioengineering, University of Texas at Dallas, Richardson, TX, 75080, USA

    Izabelle M. Gindri

  3. Laboratório de Espectroscopia e Polímeros (LEPOL), Department of Physics, Federal University of Santa Maria, UFSM, CEP: 97105-900, Santa Maria, RS, Brazil

    Marcos A. Villetti

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  1. Clarissa P. Frizzo
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  2. Caroline R. Bender
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  3. Izabelle M. Gindri
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  4. Paulo R. S. Salbego
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  6. Marcos A. P. Martins
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Correspondence to Clarissa P. Frizzo.

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Frizzo, C.P., Bender, C.R., Gindri, I.M. et al. Anion effect on the aggregation behavior of the long-chain spacers dicationic imidazolium-based ionic liquids. Colloid Polym Sci 293, 2901–2910 (2015). https://doi.org/10.1007/s00396-015-3680-y

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