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Computational Study of Iron(II) Systems Containing Ligands with Nitrogen Heterocyclic Groups

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Department of Chemistry, Wichita State University, 1854 North Fairmount, Wichita, Kansas 67260
Cite this: J. Phys. Chem. A 2007, 111, 50, 13157–13162
Publication Date (Web):November 28, 2007
Copyright © 2007 American Chemical Society

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    Density functional theory (DFT) calculations show the higher energy HOMO (highest occupied molecular orbital) orbitals of four iron(II) diimine complexes are metal centered and the lower energy LUMO (lowest unoccupied molecular orbitals) are ligand centered. The energy of the orbitals correlates with electrochemical redox potentials of the complexes. Time-dependent density functional theory (TDDFT) calculations reveal ligand centered (LC) and metal-to-ligand charge transfer (MLCT) at higher energy than experimentally observed. TDDFT calculations also reveal the presence of d−d transitions which are buried under the MLCT and LC transitions. The difference in chemical and photophysical behavior of the iron complexes compared to that of their ruthenium analogues is also addressed.

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     Author to whom correspondence should be addressed. E-mail:  [email protected].

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    The optimized geometries, the percent orbital contributions, and the calculated singlet excited-state energies of the four complexes. This material is available free of charge via the Internet at

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