Structure of Electronically Reduced N-Donor Bidentate Ligands and Their Heteroleptic Four-Coordinate Zinc Complexes: A Survey of Density Functional Theory Results.

Abstract

The role of Hartree-Fock exchange in describing the structural changes occurring upon reduction of bipyridine-based ligands and their complexes is investigated within the framework of density functional theory (DFT) calculations. A set of four free ligands in their neutral and radical anionic forms, and two of their zinc complexes in their dicationic and monocationic radical forms, is used to compare a large panel of pure, conventional, and long-range corrected hybrid DFT functionals; coupled cluster single and double calculations are used alongside experimental results as benchmarks. Particular attention has been devoted to the magnitude of the change, upon reduction, of the Δ-parameter, which measures the difference between the Cpy-Cpy and the C-N bond lengths in bipyridine ligand and is known to experimentally correlate with the charge of the ligands. Our results indicate that the structural changes significantly depend on the amount of exact exchange included in the functional. A progressive evolution is observed for the free ligands, whereas two distinct sets of results are obtained for the complexes. Functionals with a small degree of HF exchange, e.g., B3LYP, do not adequately describe geometric changes for the considered species, and, quite surprisingly, the same holds for the CC2 method. The best agreement to experimental and CCSD values is obtained with functionals that include a significant but not excessive part of exact exchange, e.g., CAM-B3LYP, M06-2X, and ωB97X-D. The calculated localization of the added electron after reduction, which depends on the self-interaction error, is used to rationalize these outcomes. Static correlation is also shown to play a role in the accurate description of the electronic structure.