Spin Crossover-Coupled Electron Transfer of [M(tacn)(2)](3+/2+) Complexes (tacn=1,4,7-Triazacyclononane; M = Cr, Mn, Fe, Co, Ni)

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The role of spin state equilibria on the thermodynamics of electron transfer in [M(tacn)(2)](3+/2+) complexes (tacn = 1,4,7-triazacyclononane; M = Cr, Mn, Fe, Co, Ni) was examined using density functional theory at the B3LYP*/cc-pVTZ(-f) level coupled to a continuum solvation model to afford excellent agreement between computed and experimental redox properties. An intuitive explanation of the previously observed nonperiodic trend in reduction potentials, which display a sawtooth pattern along the first-row transition metal series, is offered utilizing a novel diagrammatic illustration of the relationship between spin state energetics and reduction potentials. This representation leads to a generalized proposal for analyzing and designing nearly isoenergetic spin states of transition metals in a given ligand environment. A new ligand specific parameter a that allows for quantifying the differential reduction potential as a function of the metal identity is introduced, and a novel protocol is presented that divides the ligand-metal interactions into primary and secondary characteristics, which we anticipate will be useful for rationally designing the electronics of transition metal complexes in general,
Publisher
AMER CHEMICAL SOC
Issue Date
2009-05
Language
English
Article Type
Article
Keywords

SOLVATION FREE-ENERGIES; DENSITY-FUNCTIONAL THEORY; SELF-EXCHANGE RATE; MOLECULAR CALCULATIONS; REDOX POTENTIALS; STATE ENERGETICS; METAL-COMPLEXES; IRON COMPLEXES; CYTOCHROME-P450 ENZYMES; CHROMIUM(II) COMPLEXES

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.131, no.17, pp.6189 - 6197

ISSN
0002-7863
DOI
10.1021/ja809552p
URI
http://hdl.handle.net/10203/203319
Appears in Collection
CH-Journal Papers(저널논문)
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