Tight-Binding Approach to Pyrazine-Mediated Superexchange in Copper-Pyrazine Antiferromagnets.

We investigate the cause of spatial superexchange anisotropy in a family of copper-based, quasi-two-dimensional materials with very similar geometries. The compounds in this family differ mainly in their inter-layer separation but they have very different magnetic interactions, even within the basal plane. We use density functional theory and Wannier functions to parameterize two complimentary tight-binding models and show that the superexchange between the Cu2+ ions is dominated by a σ-mediated interaction between hybrid Cu-pyrazine orbitals centered on the copper atoms. We find no correlations between the strength of this exchange interaction and homologous geometric features across the compounds, such as Cu and pyrazine bond lengths and orientations of nearby counterions. We find that the pyrazine tilt angles do not affect the Cu-pyrazine-Cu exchange because the lowest unoccupied molecular orbital on pyrazine is at a very high energy (relative to the frontier orbitals, which are Cu-based). We conclude that careful control of the entire crystal structure, including non-homologous geometric features such as the inter-layer organic ligands, is vital for engineering magnetic properties.

Sensitivity of the photophysical properties of organometallic complexes to small chemical changes.

We investigate an effective model Hamiltonian for organometallic complexes that are widely used in optoelectronic devices. The two most important parameters in the model are J, the effective exchange interaction between the π and π* orbitals of the ligands, and ε*, the renormalized energy gap between the highest occupied orbitals on the metal and on the ligand. We find that the degree of metal-to-ligand charge transfer character of the lowest triplet state is strongly dependent on the ratio ε*/J. ε* is purely a property of the complex and can be changed significantly by even small variations in the complex's chemistry, such as replacing substituents on the ligands. We find that small changes in ε*/J can cause large changes in the properties of the complex, including the lifetime of the triplet state and the probability of injected charges (electrons and holes) forming triplet excitations. These results give some insight into the observed large changes in the photophysical properties of organometallic complexes caused by small changes in the ligands.