New Syntheses, Analytic Spin Hamiltonians, Structural and Computational Characterization for a Series of Tri-, Hexa- and Hepta-Nuclear Copper (II) Complexes with Prototypic Patterns

We present a series of pyrazolato-bridged copper complexes with interesting structures that can be considered prototypic patterns for tri-, hexa- and hepta- nuclear systems. The trinuclear shows an almost regular triangle with a μ3-OH central group. The hexanuclear has identical monomer units, the C...

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Published in:Chemistry an international journal 2021-03, Vol.3 (1), p.411-439
Main Authors: Toader, Ana Maria, Buta, Maria Cristina, Cimpoesu, Fanica, Toma, Andrei-Iulian, Zalaru, Christina Marie, Cinteza, Ludmila Otilia, Ferbinteanu, Marilena
Format: Article
Language:English
Subjects:
Antiferromagnetism
Aromaticity
Benzene
Bridges
Coordination compounds
Copper
Copper compounds
Density functional theory
Energy levels
Ethanol
heptanuclear complex
hexamer metallacycle
Ligands
Magnetic properties
Phenomenology
pyrazolato-bridged ligand systems
Software
spin Hamiltonian
spin models
Structural analysis
Topology
Trimers
trinuclear complex
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Summary:We present a series of pyrazolato-bridged copper complexes with interesting structures that can be considered prototypic patterns for tri-, hexa- and hepta- nuclear systems. The trinuclear shows an almost regular triangle with a μ3-OH central group. The hexanuclear has identical monomer units, the Cu6 system forming a regular hexagon. The heptanuclear can be described as two trinuclear moieties sandwiching a central copper ion via carboxylate bridges. In the heptanuclear system, the pyrazolate bridges are consolidating the triangular faces, which are sketching an elongated trigonal antiprism. The magnetic properties of these systems, dominated by the strong antiferromagnetism along the pyrazolate bridges, were described transparently, outlining the energy levels formulas in terms of Heisenberg exchange parameters J, within the specific topologies. We succeeded in finding a simple Kambe-type resolution of the Heisenberg spin Hamiltonian for the rather complex case of the heptanuclear. In a similar manner, the weak intermolecular coupling of two trimer units (aside from the strong exchange inside triangles) was resolved by closed energy formulas. The hexanuclear can be legitimately proposed as a case of coordination-based aromaticity, since the phenomenology of the six-spins problem resembles the bonding in benzene. The Broken-Symmetry Density Functional Theory (BS-DFT) calculations are non-trivial results, being intrinsically difficult at high nuclearities.
ISSN:2624-8549
2624-8549
DOI:10.3390/chemistry3010031