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Ferromagnetic coupling in copper benzimidazole chloride: structural, mass spectrometry, magnetism, and DFT studies.
- Source :
-
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2017 Dec 21; Vol. 46 (47), pp. 16663-16670. Date of Electronic Publication: 2017 Nov 23. - Publication Year :
- 2017
-
Abstract
- Herein, quasi-square planar Cu <superscript>II</superscript> (Hmbm)Cl <subscript>2</subscript> (CBC, Hmbm = (1-methyl-1H-benzo[d]imidazol-2-yl)methanol) was arranged in a pseudo orthogonal way to form Cl-bridged chains, and further ππ interactions resulted in distorted hexagonal layers. DFT calculations reveal a bond strength order of Cu-Cl > Cu-O/N ≫ CuCl. ESI-MS data reveal several small fragments from CBC, but oligomeric [Cu], [Cu], and [Cu] for non-zero in-source energies; MS data indicates the occurrence of several chemical processes, viz. splitting of the ligand, oligomerization, and redox reaction of alcohol to aldehyde and Cu <superscript>II</superscript> to Cu <superscript>I</superscript> . Gibbs free energies for the fragments were estimated using DFT. The magnetic susceptibility was modeled with the ferromagnetic coupling J(Cu-Cl2aCu) = +0.99(30) cm <superscript>-1</superscript> and J'(ππ) = +0.35(16) cm <superscript>-1</superscript> and g = 2.38(2). HF-EPR determined the anisotropic g-values, g <subscript>x</subscript> = 2.24, g <subscript>y</subscript> = 2.16, and g <subscript>z</subscript> = 2.09, and a hyperfine constant of A <subscript>z</subscript> = 450 G. DFT calculations from crystal structure data reveal a J(Cu-Cl2aCu) of +3.6 at 296 K and +4.1 cm <superscript>-1</superscript> at 90 K that dominates the magnetic properties, whereas J'(ππ) = 0.04 cm <superscript>-1</superscript> is negligibly small.
Details
- Language :
- English
- ISSN :
- 1477-9234
- Volume :
- 46
- Issue :
- 47
- Database :
- MEDLINE
- Journal :
- Dalton transactions (Cambridge, England : 2003)
- Publication Type :
- Academic Journal
- Accession number :
- 29168858
- Full Text :
- https://doi.org/10.1039/c7dt03576d