Antiferromagnetic Coupling Supported by Metallophilic Interactions: Theoretical View
Zoraida Sandoval-Olivares1, Eduardo Solis-Céspedes2,3, Dayán Páez-Hernández4,5
1Doctorado en Fisicoquímica Molecular, Universidad Andrés Bello, República 275, Santiago 8370146, Chile.
Inorganic Chemistry
|January 10, 2022
Summary
Metallophilic interactions in platinum complexes strengthen antiferromagnetic coupling. This spin polarization mechanism, involving Pt···Pt σ-bonds and p orbitals, is key for designing new magnetic materials.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Computational Chemistry
Background:
- Metallophilic interactions, particularly Pt···Pt bonds, are crucial for tuning magnetic properties in coordination complexes.
- Antiferromagnetic coupling is a key phenomenon in developing molecular magnets.
Purpose of the Study:
- To investigate the role of metallophilic interactions in supporting antiferromagnetic coupling in heterobimetallic platinum complexes.
- To elucidate the theoretical underpinnings of spin polarization mechanisms in these systems.
Main Methods:
- Broken symmetry (BS) approach for magnetic coupling calculations.
- Multiconfigurational CASSCF calculations to analyze electronic structure.
- Study of heterobimetallic complexes [PtCo(X)4(Y)]2 and [PtNi(SAc)4(H2O)]2.
Main Results:
- Calculated magnetic coupling constants agree well with experimental data.
- Axial ligands with pure σ-donor character enhance antiferromagnetic coupling.
- A weak Pt···Pt σ(dz2...dz2) bond contributes to stabilization via spin polarization.
- Spin polarization involves d and empty 6p orbitals of platinum, enhancing magnetic orbital delocalization.
Conclusions:
- Metallophilic interactions significantly influence antiferromagnetic coupling strength.
- Spin polarization mechanism is driven by a combination of orbital interactions and delocalization.
- Findings are relevant for designing molecular systems with tunable magnetic properties based on metallophilic interactions.
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