Skip to main content
SpringerLink
Log in

DFT and MM description of the structure and magnetic properties of manganese complexes with X-phenylcyanamido bridging ligand

  • Original Paper
  • Published:
Monatshefte für Chemie - Chemical Monthly Aims and scope Submit manuscript

Abstract

Magnetic properties of the complexes [Mn(3-Clpcyd)(H2O)-(phen)2]+, [{Mn(3-Fpcyd)(MeOH)(phen)}2(μ-3-Fpcyd)2], [{Mn(3-Fpcyd)(EtOH)(phen)}2(μ-3-Fpcyd)2], [{Mn(3-Clpcyd)(MeOH)(phen)}2(μ-3-Clpcyd)2], and [{Mn(4-Clpcyd)(EtOH)(phen)}2(μ-4-Clpcyd)2] (where Xpcyd = halogeno-phenylcyanamido; phen = 1,10-phenanthroline) have been explored by means of density functional theory (DFT). Exchange coupling constants were calculated from the energy differences between the high-spin and broken-symmetry states. Very good agreement between theoretical and experimental data was achieved. The g-tensor calculations were performed employing the coupled perturbed Kohn–Sham equations. Molecular mechanics calculations have been performed to elucidate structural features in the five complexes. Finally, the reliability of the molecular mechanics results was confirmed by comparing the magnetic couplings calculated on optimized structures with experimental data.

Graphical Abstract

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

Similar content being viewed by others

References

  1. Rajaraman G, Totti F, Bencini A, Caneschi A, Sessoli R, Gatteschi D (2009) Dalton Trans 45:3153

    Article  Google Scholar 

  2. Bencini A, Casarin M, Forrer D, Franco L, Garau F, Masciocchi N, Pandolfo L, Pettinari C, Ruzzi M, Vittadini A (2009) Inorg Chem 48:4044

    Article  CAS  Google Scholar 

  3. Bencini A, Totti F (2009) J Chem Theory Comput 5:44

    Article  Google Scholar 

  4. Bencini A, Totti F (2005) Int J Quantum Chem 101:819

    Article  CAS  Google Scholar 

  5. Duboc C, Ganyushin D, Sivalingam K, Collomb MN, Neese F (2010) J Phys Chem 114:10750

    CAS  Google Scholar 

  6. Pantazis DA, Kremwald V, Orio M, Neese F (2010) Dalton Trans 39:4959

    Article  CAS  Google Scholar 

  7. Orio M, Pantazis DA, Petrenko T, Neese F (2009) Inorg Chem 48:7251

    Article  CAS  Google Scholar 

  8. Ruiz E, Rodríguez-Fortea A, Cano J, Alvarez S, Alemany P (2003) J Comput Chem 24:982

    Article  CAS  Google Scholar 

  9. Kahn O (1993) Molecular magnetism. VCH, New York

    Google Scholar 

  10. Neese F (2009) Coord Chem Rev 253:526

    Article  CAS  Google Scholar 

  11. Pryce MHL (1950) Phys Rev 80:1107

    Article  CAS  Google Scholar 

  12. Abragam A, Pryce MHL (1951) Proc Roy Soc 205:135

    Article  CAS  Google Scholar 

  13. Noodleman L, Peng CY, Case DA, Mouesca JM (1995) Coord Chem Rev 144:199

    Article  CAS  Google Scholar 

  14. Noodleman L, Case DA, Aizman A (1988) J Am Chem Soc 110:1001

    Article  CAS  Google Scholar 

  15. Noodleman L, Norman JG, Osborne JH, Aizman A, Case DA (1985) J Am Chem Soc 107:3418

    Article  CAS  Google Scholar 

  16. Noodleman L (1981) J Chem Phys 74:5737

    Article  CAS  Google Scholar 

  17. Soda T, Kitagawa Y, Onishi T, Takano Y, Shigeta Y, Nagao H, Yoshika Y, Yamaguchi K (2000) Chem Phys Lett 319:223

    Article  CAS  Google Scholar 

  18. Yamaguchi K, Takahara Y, Fueno T (1986) App Quantum Chem 155

  19. Neese F (2003) Curr Opin Chem Biol 7:125

    Article  CAS  Google Scholar 

  20. Neese F (2001) J Chem Phys 115:11080

    Article  CAS  Google Scholar 

  21. Koseki S, Schmidt MW, Gordon MS (1998) J Phys Chem 102:10430

    CAS  Google Scholar 

  22. Koseki S, Schmidt MW, Gordon MS, Matsunaga N (1995) J Phys Chem 99:12764

    Article  CAS  Google Scholar 

  23. Koseki S, Schmidt MW, Gordon MS (1992) J Phys Chem 96:10768

    Article  CAS  Google Scholar 

  24. Bencini A, Gatteschi D (1990) EPR of exchange coupled systems. Springer, New York

    Google Scholar 

  25. Neese F (2004) In: Calculation of NMR and EPR parameters, theory and applications. Wiley-VCH, Weinheim

  26. Neese F (2007) J Chem Phys 127:164112

    Article  Google Scholar 

  27. Ray K, Begum A, Weyhermuller T, Piligkos S, van Slageren J, Neese F, Wieghardt K (2005) J Am Chem Soc 127:4403

    Article  CAS  Google Scholar 

  28. Crutchley RJ (2001) Coord Chem Rev 125:219

    Google Scholar 

  29. Escuer A, Sanz N, Vicente R, Mautner FA (2003) Inorg Chem 42:541

    Article  CAS  Google Scholar 

  30. Escuer A, Sanz N, Vicente R, Mautner FA (2003) Dalton Trans 11:2121

    Article  Google Scholar 

  31. Escuer A, Mautner FA, Sanz N, Vicente R (2004) Polyhedron 23:1409

    Article  CAS  Google Scholar 

  32. Duboc C, Collomb MN, Neese F (2010) Appl Magn Reson 37:229

    Article  Google Scholar 

  33. Zein S, Duboc C, Lubitz W, Neese F (2008) Inorg Chem 47:134

    Article  CAS  Google Scholar 

  34. Duboc C, Collomb MN, Pécaunt J, Deronzier A, Neese F (2008) Chem Eur J 14:6498

    Article  CAS  Google Scholar 

  35. Pederson MR, Khanna SN (1999) Phys Rev 60:9566

    Article  CAS  Google Scholar 

  36. Neese F (2006) Orca, an ab initio, DFT, and Semiempirical Electronic Structure Package, Version 2.8, Revision 15. Max-Planck-Institute für Bioanorganische Chemie, Mulhein

    Google Scholar 

  37. Vosko S, Wilk L, Nusair M (1980) Can J Phys 58:1200

    Article  CAS  Google Scholar 

  38. Handy NC, Cohen AJ (2001) Mol Phys 99:403

    Article  CAS  Google Scholar 

  39. Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 77:3865

    Article  CAS  Google Scholar 

  40. Schaefer A, Horn H, Ahlrichs R (1992) J Chem Phys 97:2571

    Article  CAS  Google Scholar 

  41. Schaefer A, Huber C, Ahlrichs R (1994) J Chem Phys 100:5829

    Article  CAS  Google Scholar 

  42. Becke AD (1986) J Chem Phys 84:4524

    Article  CAS  Google Scholar 

  43. Perdew JP, Yue W (1986) Phys Rev 33:88001

    Google Scholar 

  44. Becke AD (1988) Phys Rev 38:3098

    Article  CAS  Google Scholar 

  45. Perdew JP (1986) Phys Rev 33:8822

    Article  Google Scholar 

  46. Kutzelnigg W, Fleischer U, Schindler M (1990) The IGLO-method: ab initio calculation and interpretation of NMR chemical shifts and magnetic susceptibilities. Springer, Heidelberg

    Google Scholar 

  47. Grubisic S, Gruden M, Niketic SR, Sakagami N, Kaizaki S (2002) J Mol Struct 609:1

    Article  CAS  Google Scholar 

  48. Niketić SR, Rasmussen KJ (1977) The consistent force field: a documentation. Lecture notes in chemistry. Springer, Berlin, Germany

Download references

Acknowledgments

This work was financially supported by the Serbian Ministry for Science through grant no. 172035.

Author information

Authors and Affiliations

  1. Center for Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, P.O. Box 815, 11001, Belgrade, Serbia

    Marko Perić, Svetozar Niketić, Matija Zlatar & Sonja Grubišić

  2. Faculty of Chemistry, University of Belgrade, Studentski trg 16, P.O. Box 158, 11001, Belgrade, Serbia

    Maja Gruden-Pavlović

Authors
  1. Marko Perić
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Svetozar Niketić
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Matija Zlatar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Maja Gruden-Pavlović
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sonja Grubišić
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sonja Grubišić.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 123 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Perić, M., Niketić, S., Zlatar, M. et al. DFT and MM description of the structure and magnetic properties of manganese complexes with X-phenylcyanamido bridging ligand. Monatsh Chem 142, 585–592 (2011). https://doi.org/10.1007/s00706-011-0502-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00706-011-0502-x

Keywords

Search

Navigation