Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him) 6 ] {Cu(Him) 4 [Cu(μ-EDTA)(Him)] 2 }·6H 2 O (1) as the Novel Imidazolium(+) Salt (H 2 im) 2 [Cu(Him) 4 {(µ-EDTA)Cu(Him)} 2 ]·2H 2 O (2)-A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations.

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  • Additional Information
    • Source:
      Publisher: MDPI Country of Publication: Switzerland NLM ID: 101092791 Publication Model: Electronic Cited Medium: Internet ISSN: 1422-0067 (Electronic) Linking ISSN: 14220067 NLM ISO Abbreviation: Int J Mol Sci Subsets: MEDLINE
    • Publication Information:
      Original Publication: Basel, Switzerland : MDPI, [2000-
    • Subject Terms:
      Copper*/chemistry ; Imidazoles*/chemistry ; Anions*/chemistry; Crystallography, X-Ray ; Edetic Acid/chemistry ; Density Functional Theory ; Models, Molecular ; Spectroscopy, Fourier Transform Infrared ; Molecular Structure ; Coordination Complexes/chemistry ; Hydrogen Bonding ; Salts/chemistry ; Magnetic Phenomena ; Magnetics
    • Abstract:
      Inspired by the reported crystal structure of compound 1 , we aimed to synthesize and determine the structure of compound 2 , where two imidazolium (H 2 im + ) ions serve as diamagnetic countercations. Here, we report the thermal stabilities, FT-IR, visible, and RSE spectra, as well as the magnetic properties of both compounds. In these structures, µ-EDTA acts as a pentadentate chelator for both terminal Cu centers within the centrosymmetric linear trinuclear anion. The Cu(µ-EDTA) chelates bind to the central Cu(Him) 4 unit in subtly different ways: in compound 1 , µ-EDTA has a free acetate arm and binds the central Cu(II) center through a syn,anti-carboxylate group. In contrast, in compound 2 , the non-chelating acetate arm serves as a monodentate O-donor to the central Cu(II) atom, increasing the Cu(terminal)···Cu(central) distance from 6.08 Å in 1 to 6.80 Å in 2 . Additionally, pairs of H 2 im + ions in compound 2 display antiparallel π-stacking interactions. We conclude that the H 2 im + counterions in compound 2 enable the magnetic isolation of the nearly identical trinuclear anion present in both compounds. DFT calculations further support the role of different interactions in stabilizing each crystal structure. In compound 2 , dominant contributions from N-H···O hydrogen bonds and π-stacking interactions are accompanied by other, less conventional interactions, such as multiple C-H···O contacts and an O···CO(π-hole) interaction within the trinuclear anion.
    • Grant Information:
      PID2020-115637GB-I00 and PID2023-148453NB-I00 Ministerio de Ciencia, Innovación y Universidades
    • Contributed Indexing:
      Keywords: DFT calculations; copper(II); crystal structure; linear trinuclear complex; magnetism; spectral properties; thermogravimetry
    • Accession Number:
      789U1901C5 (Copper)
      0 (Imidazoles)
      0 (Anions)
      9G34HU7RV0 (Edetic Acid)
      0 (Coordination Complexes)
      0 (Salts)
    • Publication Date:
      Date Created: 20241217 Date Completed: 20241217 Latest Revision: 20241217
    • Publication Date:
      20241217
    • Accession Number:
      10.3390/ijms252313130
    • Accession Number:
      39684840