ic5b01409_si_002.xyz (136.17 kB)
Tuning the Electronic Structure of Fe(II) Polypyridines via Donor Atom and Ligand Scaffold Modifications: A Computational Study
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posted on 2015-09-08, 00:00 authored by David
N. Bowman, Alexey Bondarev, Sriparna Mukherjee, Elena JakubikovaFe(II)
polypyridines are an important class of pseudo-octahedral
metal complexes known for their potential applications in molecular
electronic switches, data storage and display devices, sensors, and
dye-sensitized solar cells. Fe(II) polypyridines have a d6 electronic configuration and pseudo-octahedral geometry and can
therefore possess either a high-spin (quintet) or a low-spin (singlet)
ground state. In this study, we investigate a series of complexes
based on [Fe(tpy)2]2+ (tpy = 2,2′;6′,2″-terpyridine)
and [Fe(dcpp)2]2+ (dcpp = 2,6-bis(2-carboxypyridyl)pyridine).
The ligand field strength in these complexes is systematically tuned
by replacing the central pyridine with five-membered (N-heterocyclic
carbene, pyrrole, furan) or six-membered (aryl, thiazine-1,1-dioxide,
4-pyrone) moieties. To determine the impact of ligand substitutions
on the relative energies of metal-centered states, the singlet, triplet,
and quintet states of the Fe(II) complexes were optimized in water
(PCM) using density functional theory at the B3LYP+D2 level with 6-311G*
(nonmetals) and SDD (Fe) basis sets. It was found that the dcpp ligand
scaffold allows for a more ideal octahedral coordination environment
in comparison to the tpy ligand scaffold. The presence of six-membered
central rings also allows for a more ideally octahedral coordination
environment relative to five-membered central rings, regardless of
the ligand scaffold. We find that the ligand field strength in the
Fe(II) polypyridines can be tuned by altering the donor atom identity,
with C donor atoms providing the strongest ligand field.
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complexdcpp ligand scaffoldElectronic StructureLigand Scaffold Modificationstpy ligand scaffoldligand field strengthPCMdata storageDonor Atomquintet statesC donor atomsligand fieldFepolypyridineligand substitutionsground statebasis setsdisplay devicesB 3LYP leveloctahedral coordination environmentdonor atom identityligand scaffoldSDD
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