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Date of Award


Document Type

Dissertation - Pacific Access Restricted

Degree Name

Doctor of Philosophy (Ph.D.)



First Advisor

Larry Spreer

First Committee Member

Michael McCallum

Second Committee Member

Silvio Rodriguez

Third Committee Member

Cindy Krysac


The local structures of the iron atoms for a series of strongly coupled Fe 2 (TIED)L 4 complexes (TIED = tetraiminethylenedimacrocycle, L = axail ligand) have been investigated by K-edge X-ray Absorption Spectroscopy (XAS). These complexes include not only the well characterized iso-valence CH 3 CN complex, mixed-valence CH 3 CN and Cl − complexes, and previously reported iso-valence CO complex but also the new isolated solids of iso-valence Fe 2 TIED complexes with Cl − , Br − , imidazole, pyridine, histidine, N,N-dimethyformamide (DMF), SCN − , and CN − as axial ligands and mixed-valence complexes with Br − and imidazole as axial ligands. The average Fe-N distances for the first coordination sphere of the iron atom obtained by EXAFS analysis are 1.94, 1.94, 1.95, 1.96, 1.94, 1.93, 1.96, 1.96, 1.96, and 1.96 Å for the iso- and mixed-valence CH 3 CN and imidazole complexes and iso-valence complexes with SCN − , CN − , CO, pyridine, histidine, and DMF as axial ligands, respectively. Two-shell fitting analyses of the complexes gave average iron to the four planar coordinated nitrogen distance of 1.90, 1.91, 1.91, 1.92, and 1.92 Å for the Fe 2 (TIED)L 4 with L = DMF, pyridine, Cl − , Br − , imidazole, and histidine complexes, respectively. The average distances from the center iron to: N(DMF), 2.05; N(pyridine), 2.05; Cl − , 2.33; Br − , 2.45; N(imidazole), 2.08; and N(histidine), 2.07 Å. They are all comparable to related bond distances in the literature. The above data indicate that there is no significant difference in the average Fe-N distances between each of the iso- and mixed-valence pairs. Also different axial ligands do not cause significant impact on the average Fe-N distances from the iron atom to the four coordinated N in the TIED ligand. The threshold edge positions shift about +1 eV from the iso-valence CH 3 CN, Cl − , and Br − complexes to their corresponding mixed-valence complexes. The relatively small shift compared with the normal +2 [special characters omitted] +3 eV edge shift from Fe 2+ to Fe 3+ reflects the oxidation state change of iron from Fe 2+ to Fe 2.5+ . The edge energy of the isovalence diiron complexes with different axial ligands increases in the order of the spectrochemical series of the axial Iigands from strong to weak field Iigands as follows [58, 59]: [special characters omitted] All the complexes studied here have a weak dipole-forbidden 1s → 3d pre-edge transition. The low intensity indicates only a small distortion of the octahedral coordination geometry of the central iron atom.




9780599940147 , 059994014X

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