Skip to main content
SpringerLink
Log in

Solvatochromism of a Novel Ruthenium Complex, [Ru(acac)2(N-(2-Methylsulfonylphenyl)formamido)]: A Correlation between the Electronic Structure and Spectroscopic Properties

  • STRUCTURE OF MATTER AND QUANTUM CHEMISTRY
  • Published:
Russian Journal of Physical Chemistry A Aims and scope Submit manuscript

Abstract

Solvatochromism is commonly used in many fields of chemical and biological research to study bulk and local polarity in macro systems (membranes, etc.), or even the conformation and binding of proteins. Despite its wide use, solvatochromism still remains a largely unknown phenomenon due to the extremely complex coupling of many different interactions and dynamical processes which characterize it. In this work the spectroscopic characterization of the Ru(acac)2(L) complex (1) [HL = N-(2-methylsulfonyl-phenyl)formamide] are presented. Gas- and solution-phase structural and electronic features of (acac)2Ru(L) have been investigated using density functional theory. The molecular structure underscores the flexibility of the formyl fragment in the metal complex. Time-dependent density functional theory has been used to investigate the excited states and solvatochromic properties of Ru(acac)2(L). The calculated vertical excitation energies in solution are consistent with the experimental data, showing that the ligand-to-metal charge-transfer transitions, in both the visible and UV regions, dominate over the ligand based π–π* transitions.

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

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.

Similar content being viewed by others

REFERENCES

  1. A. B. P. Lever, in Inorganic Electronic Spectroscopy, 2nd ed. (Elsevier, Amsterdam, 1984), p. 208.

    Google Scholar 

  2. A. Kundt, Ann. Phys. Chem., N. F. 4, 34 (1878); Chem. Zentralbl., 498 (1878); G. Scheibe, E. Felger, and G. Rossler, Ber. Dtsch. Chem. Ges. (1927); S. E. Sheppard, Rev. Mod. Phys. 14, 303 (1942).

    Article  Google Scholar 

  3. C. Reichardt, Solvent and Solvent Effects in Organic Chemistry, 3rd ed. (Wiley-VCH, Weinheim, 2002); P. Suppan and N. Ghoneim, Solvatochromism (The Royal Society of Chemistry, Cambridge, 1997).

  4. S. R. Marder, D. N. Beratan, and L. T. Cheng, Science (Washington, DC, U. S.) 252, 103 (1991); S. R. Marder, C. B. Gorman, F. Meyers, J. W. Perry, G. Bourhill, J. L. Bredas, and B. M. Pierce, Science 265, 632 (1994); F. Meyers, S. R. Marder, B. M. Pierce, and J. L. Bredas, J. Am. Chem. Soc. 116, 10703 (1994); T. J. Marks and M. A. Ratner, Angew. Chem. 34, 155 (1995); C. B. Gorman and S. R. Marder, Proc. Natl. Acad. Sci. U. S. A. 90, 11297 (1993).

    Article  Google Scholar 

  5. S. R. Marder, in Inorganic Materials, Ed. by D. W. Bruce and D. O’Hare (Wiley, Chichester, U.K., 1992); D. R. Kanis, M. A. Ratner, and T. J. Marks, Chem. Rev. 94, 195 (1994); N. J. Long, Angew. Chem., Int. Ed. Engl. 34, 21 (1995).

  6. D. R. Kanis, M. A. Ratner, and T. J. Marks, J. Am. Chem. Soc. 112, 8203 (1990); D. R. Kanis, M. A. Ratner, and T. J. Marks, Chem. Mater. 3, 19 (1991); D. R. Kanis, M. A. Ratner, and T. J. Marks, J. Am. Chem. Soc. 114, 10338 (1992); D. R. Kanis, P. G. Lacroix, M. A. Ratner, and T. J. Marks, J. Am. Chem. Soc. 116, 10089 (1994).

    Article  CAS  Google Scholar 

  7. M. Schröder and T. A. Stephenson, in Comprehensive Coordination Chemistry, Ed. by G. Wilkinson, R. D. Gillard, and J. A. McCleverty (Pergamon, Oxford, U.K., 1987), Vol. 4.

    Google Scholar 

  8. S. Chatterjee, Transition Metal Complex of Redox Non-Innocent N,S Mixed-Donor Ligand (Scholar’s Press, Germany, 2014).

    Google Scholar 

  9. S. Chatterjee, S. Mandal, S. Samanta, and S. Goswami, Dalton Trans. 41, 7057 (2012).

    Article  CAS  Google Scholar 

  10. G. t. Velde, F. M. Bickelhaupt, E. J. Baerends, C. F. Guerra, S. J. A. v. Gisbergen, J. G. Snijders, and T. Ziegler, J. Comput. Chem. 22, 931 (2001), ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands. http://www.scm.com.

  11. M. J. Frisch et al., Gaussian 03 (Gaussian Inc., Pittsburgh, PA, 2003).

  12. A. D. Becke, Phys. Rev. A 38, 3098 (1988).

    Article  CAS  Google Scholar 

  13. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).

    Article  CAS  Google Scholar 

  14. A. Klamt and G. Schüürmann, J. Chem. Soc., Perkin Trans. 2, 799 (1993), A. Klamt and V. Jonas, J. Chem. Phys. 105, 9972 (1996).

    Article  CAS  Google Scholar 

  15. C. C. Pye and T. Ziegler, Theor. Chem. Acc. 101, 396 (1999).

    Article  CAS  Google Scholar 

  16. S. Miertuš, E. Scrocco, and J. Tomasi, Chem. Phys. 55, 117 (1981); M. Cossi, V. Barone, R. Cammi, and J. Tomasi, Chem. Phys. Lett. 255, 327 (1996).

    Article  Google Scholar 

  17. A. D. Becke, J. Chem. Phys. 98, 1372 (1993).

    Article  CAS  Google Scholar 

  18. A. L. Tenderholt, QMForge: A Program to Analyze Quantum Chemistry Calculations. Version 2.1. http://qmforge.sourceforge.net.

  19. M. J. Kamlet, J.-L. M. Abboud, and R. W. Taft, J. Am. Chem. Soc. 99, 6027 (1977).

    Article  CAS  Google Scholar 

  20. A. Masternak, G. Wenska, J. Milecki, B. Skalski, and S. Franzen, J. Phys. Chem. A 109, 759 (2005).

    Article  CAS  Google Scholar 

  21. S. L. Murov, I. Carmichael, and G. L. Hug, Handbook of Photochemistry, 2nd ed. (Marcel Dekker, New York, 1993).

    Google Scholar 

  22. E. Kosover, J. Am. Chem. Soc. 80, 3253 (1958).

    Article  Google Scholar 

  23. C. Reichardt, Angew. Chem., Int. Ed. Engl. 4, 29 (1965), C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed. (Wiley-VCH, Weinheim, Germany, 1988); J. Catalán, J. Org. Chem. 62, 8231 (1997).

  24. Y. Marcus, Chem. Soc. Rev. 22, 409 (1993).

    Article  CAS  Google Scholar 

  25. V. N. Nemykin and P. Basu, Inorg. Chem. 42, 4046 (2003); R. L. McNaughton, S. Mondal, V. N. Nemykin, P. Basu, and M. L. Kirk, Inorg. Chem. 44, 8216 (2005); F. Wang and T. Ziegler, Mol. Phys. 102, 2585 (2004); V. N. Nemykin, J. G. Olsen, E. Perera, and P. Basu, Inorg. Chem. 45, 3557 (2006).

    Article  CAS  Google Scholar 

  26. F. Aquilante, M. Cossi, O. Crescenzi, G. Scalmani, and V. Barone, Mol. Phys. 101, 1945 (2003).

    Article  CAS  Google Scholar 

Download references

ACKNOWLEDGMENTS

SC thanks Dr. Prosenjit Seal for his thoughtful inputs in carrying out the works and some valuable help. SC also thanks Scholar’s Press to give the permission to publish the data, mentioned in the book “Transition Metal Complex of Redox Non-Innocent N,S Mixed-Donor Ligand” published by the same author, in this article.

Author information

Authors and Affiliations

  1. Department of Chemistry, Serampore College, 712201, Serampore, Hoogly, West Bengal, India

    Sudipta Chatterjee

Authors
  1. Sudipta Chatterjee
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sudipta Chatterjee.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sudipta Chatterjee Solvatochromism of a Novel Ruthenium Complex, [Ru(acac)2(N-(2-Methylsulfonylphenyl)formamido)]: A Correlation between the Electronic Structure and Spectroscopic Properties. Russ. J. Phys. Chem. 94, 789–799 (2020). https://doi.org/10.1134/S0036024420040202

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0036024420040202

Keywords:

Search

Navigation