Journal of Molecular Modeling

, 22:301 | Cite as

Coordination complexes of 4-methylimidazole with ZnII and CuII in gas phase and in water: a DFT study

  • Malek Boukallaba
  • Boutheïna Kerkeni
  • Christine Lepetit
  • Dorothée BerthomieuEmail author
Original Paper
Part of the following topical collections:
  1. Festschrift in Honor of Henry Chermette


A quantum chemistry study of mononuclear metal coordination with four 4-methylimidazole ligands (4-MeIm) was investigated. The four complexes [Cu(4-MeIm)4]2+, [Cu(4-MeIm)4, H2O]2+, [Zn(4-MeIm)4]2+ and [Zn(4-MeIm)4, H2O]2+ were studied with particular attention to the Nπ or Nτ possible coordinations of the 4-MeIm ring with the metals, using different DFT methods. The results suggest that the Nτ coordination of 4-MeIm ring to ZnII or CuII is more favorable whatever the level of calculation. In contrast, the addition of one water molecule in the first coordination sphere of the metal ions provides five-coordinated complexes showing no Nπ or Nτ preferences. There is good agreement between the DFT-calculated structure and those available experimentally. When metal ions are four-fold coordinated, they adopt a tetrahedral geometry. When CuII and ZnII are five-fold coordinated, highly symmetric structures or intermediate structures are calculated. Similar energies are calculated for different structures, suggesting flat potential energy surfaces. The addition of implicit solvent modifies the calculated first coordination sphere, especially for [Cu(4-MeIm)4, H2O]2+ structures. The QTAIM and ELF topological analyses of the interaction between CuII and the neutral ligands, clearly indicate a dative bonding with a strong ionic character.


Coordination complexes with ZnII or CuII 4-methylimidazole and water Histidine Implicit solvents DFT QTAIM ELF topological analyses 



Calculations (projects x2015087394 and x2016087394) were carried out on the IBM SP4 computers of the CINES (Centre Informatique National de l’Enseignement Supérieur) in Montpellier (France) and of the IDRIS (Institut des Ressources en Informatique Scientifique) in Orsay (France). MB is grateful to MESRS (Ministère de l’Enseignement Supérieur et de la Recherche Scientifique), Tunisia for an 11-month grant.

Supplementary material

894_2016_3167_MOESM1_ESM.docx (280 kb)
ESM 1 (DOCX 279 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.Departement de Physique Laboratoire de Physique de la Matière Condensée (LPMC) Faculté des Sciences de TunisUniversité de Tunis El ManarTunisTunisia
  2. 2.Institut Charles Gerhardt, MACS, UMR 5253 CNRS-ENSCM-UMMontpellier Cedex 5France
  3. 3.Université de la Manouba, Institut Supérieur des Arts Multimédia de la Manoubala ManoubaTunisia
  4. 4.CNRS, LCC (Laboratoire de Chimie de Coordination)Toulouse Cedex 4France
  5. 5.Université de Toulouse, UPS, INPTToulouse Cedex 4France
  6. 6.LPCNO, UMR 5215 CNRS-INSA-UPSToulouse Cedex 4France

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