Skip to main content
SpringerLink
Log in

Solute-Solvent Interactions in Solutions of Solvatochromic Phenoxides: A Dynamics Simulation Study

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Solute-solvent interactions in protic (water, methanol and 2-propanol) and aprotic (DMSO) solvents of four solvatochromic phenoxides, the 4- and 2-pyridiniophenoxides, Brooker’s merocyanine and the N-methyloxyquinolinium betaine, were investigated with the aid of molecular dynamics simulations. Although the size of the first solvation shell of the phenoxide oxygen of all betaines remains constant in the three protic solvents, it comprises increasingly fewer solvent molecules as the volume of the hydroxylic solvent increases. In DMSO, the donor phenoxide group of the 4-pyridiniophenoxide betaine is loosely solvated, leading to an internal charge-transfer with smaller transition energies than in protic media.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Reichardt, C.: Solvatochromic dyes as solvent polarity indicators. Chem. Rev. 94, 2319–2358 (1994)

    Article  CAS  Google Scholar 

  2. González, D., Neilands, O., Rezende, M.C.: The solvatochromic behaviour of 2-and 4-(N-pyridinio)phenoxides. J. Chem. Soc. Perkin Trans. 2, 713–717 (1999)

    Google Scholar 

  3. Tada, E.B., Silva, P.L., El Seoud, O.A.: Thermo-solvatochromism of zwitterionic probes in aqueous alcohols: effects of the properties of the probe and the alcohol. Phys. Chem. Chem. Phys. 5, 5378–5385 (2003)

    Article  CAS  Google Scholar 

  4. Bosch, E., Rosés, M., Herodes, K., Koppel, I., Leito, I., Koppel, I., Taal, V.: Solute-solvent and solvent-solvent interactions in binary solvent mixtures. 2. Effect of temperature on the ET(30) polarity parameter of dipolar hydrogen bond acceptor-hydrogen bond donor mixtures. J. Phys. Org. Chem. 9, 403–410 (1996)

    Article  CAS  Google Scholar 

  5. Wu, Y.G., Tabata, M., Takamuku, T.: Preferential solvation in aqueous-organic mixed solvents using solvatochromic indicators. J. Solution Chem. 31, 381–395 (2002)

    Article  CAS  Google Scholar 

  6. Silva, P.L., Bastos, E.L., El Seoud, O.A.: Solvation in binary mixtures of water and polar aprotic solvents: theoretical calculations of the concentrations of solvent-water hydrogen-bonded species and application to thermosolvatochromism of polarity probes. J. Phys. Chem. B 111, 6173–6180 (2007)

    Article  CAS  Google Scholar 

  7. Mente, S.R., Maroncelli, M.: Computer simulations of the solvatochromism of betaine-30. J. Phys. Chem. B 103, 7704–7719 (1999)

    Article  CAS  Google Scholar 

  8. Lobaugh, J., Rossky, P.J.: Solvent and intramolecular effects on the absorption spectrum of betaine-30. J. Phys. Chem. A 104, 899–907 (2000)

    Article  CAS  Google Scholar 

  9. Hernandes, M.Z., Longo, R., Coutinho, K., Canuto, S.: Solute relaxation on the solvatochromism of ortho-betaine dyes. A sequential Monte Carlo/quantum mechanics study. Phys. Chem. Chem. Phys. 6, 2088–2092 (2004)

    Article  Google Scholar 

  10. Fonseca, T.L., Coutinho, K., Canuto, S.: Polarization and solvatochromic shift of ortho-betaine in water. Chem. Phys. 349, 109–114 (2008)

    Article  CAS  Google Scholar 

  11. Dimroth, K., Reichardt, C., Siepmann, T., Bohlmann, F.: Über pyridinium-N-phenol-betaine und ihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln. Justus Liebigs Ann. Chem. 661, 1–37 (1963)

    Article  CAS  Google Scholar 

  12. Jacques, P.: On the relative contributions of non-specific and specific interactions to the unusual solvatochromism of a typical merocyanine dye. J. Phys. Chem. 90, 5535–5539 (1986)

    Article  CAS  Google Scholar 

  13. Morley, J.O., Morley, R.M., Docherty, R., Charlton, M.H.: Fundamental studies on Brooker’s merocyanine. J. Am. Chem. Soc. 119, 10192–10202 (1997)

    Article  CAS  Google Scholar 

  14. Baraldi, I., Brancolini, G., Momicchioli, F., Ponterini, G., Vanossi, D.: Solvent influence on absorption and fluorescence spectra of merocyanine dyes: a theoretical and experimental study. Chem. Phys. 288, 309–325 (2003)

    Article  CAS  Google Scholar 

  15. Reichardt, C.: Solvents and Solvent Effects in Organic Chemistry, 3rd edn, pp. 344, 345. VCH-Wiley, Weinheim (2003)

    Google Scholar 

  16. Ueda, M., Schelly, Z.A.: Reverse micelles of Aerosol-OT in benzene. 4. Investigation of the micropolarity using 1-methyl-8-oxyquinolinium betaine as probe. Langmuir 5, 1005–1008 (1989)

    Article  CAS  Google Scholar 

  17. Da Silva, D.C., Ricken, I., Silva, M.A.R., Machado, V.G.: Solute-solvent and solvent-solvent interactions in the preferential solvation of Brooker’s merocyanine in binary solvent mixtures. J. Phys. Org. Chem. 15, 420–427 (2002)

    Article  CAS  Google Scholar 

  18. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A. Jr., Stratmann, R.E., Burant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Baboul, A.G., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Gonzalez, C., Challacombe, M., Gill, P.M.W., Johnson, B.G., Chen, W., Wong, M.W., Andres, J.L., Head-Gordon, M., Replogle, E.S., Pople, J.A.: Gaussian 98. Gaussian Inc., Pittsburgh (1998)

    Google Scholar 

  19. Martínez, J.M., Martínez, L.: Packing optimization for automated generation of complex system’s initial configurations for molecular dynamics and docking. J. Comput. Chem. 24, 819–825 (2003)

    Article  Google Scholar 

  20. Brooks, B.R., Bruccoleri, R.E., Olafson, B.D., States, D.J., Swaminathan, S., Karplus, M.: CHARMM: A program for macromolecular energy, minimization, and dynamics calculations. J. Comput. Chem. 4, 187–217 (1983)

    Article  CAS  Google Scholar 

  21. InsightII User Guide. Accelrys, San Diego (1998)

  22. Pedretti, A., Villa, L., Vistoli, G.: VEGA- An open platform to develop chemo-bio-informatics applications, using plug-in architecture and script programming. J. Comput.-Aided Mol. Des. 18, 167–173 (2004)

    Article  CAS  Google Scholar 

  23. Phillips, J.C., Braun, R., Wang, W., Gumbart, J., Tajkhorshid, E., Villa, E., Chipot, C., Skeel, R.D., Kalé, L., Schulten, K.: Scalable molecular dynamics with NAMD. J. Comput. Chem. 26, 1781–1802 (2005)

    Article  CAS  Google Scholar 

  24. Humphrey, W., Dalke, A., Schulten, K.: VMD: Visual molecular dynamics. J. Mol. Graphics 14, 33–38 (1996)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Facultad de Química y Biología, Universidad de Santiago, Casilla 40, Correo 33, Santiago, Chile

    Carolina Mascayano, Marcos Caroli Rezende, Carolina Mendez, Gabriel Núñez & Valeska Chiang

Authors
  1. Carolina Mascayano
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Marcos Caroli Rezende
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Carolina Mendez
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gabriel Núñez
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Valeska Chiang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Marcos Caroli Rezende.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mascayano, C., Rezende, M.C., Mendez, C. et al. Solute-Solvent Interactions in Solutions of Solvatochromic Phenoxides: A Dynamics Simulation Study. J Solution Chem 38, 363–371 (2009). https://doi.org/10.1007/s10953-009-9369-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-009-9369-4

Keywords

Search

Navigation