Perturbation of the electronic structure of the Creutz-Taube ion via asymmetric encapsulation with macrocyclic ether species

Journal Article · Wed May 19 04:00:00 EDT 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00063a073· OSTI ID:6297842

Dong, Y; Hupp, J T; Yoon, D I ^[1]

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1. Northwestern Univ., Evanston, IL (United States)

Ligand-bridged mixed-valence ions can exist in either valence-localized double-minimum ground potential energy surface or valence-delocalized (single-minimum ground PE surface) form. The determining factor is the balance between twice the initial-state/final-state electroniccoupling energy (H[sub if]) and the sum of the zeroth-order reorganization or trapping energy ([chi]) and any redox asymmetry [delta]E. For the Creutz-Taube ion (NH[sub 3])[sub 5[minus]] Ru[sup 11][sup 1/2](NH[sub 3])[sub 5][sup 5+], (1), redox asymmetry is absent, the valencies are completely delocalized, and 2H[sub if] evidently exceeds [epsilon]. We reasoned, however, that [open quotes]electronic isomerization[close quotes] to a valence-localized form might be possible if significant redox asymmetry could be introduced. We report here the introduction of the desired asymmetry in an unusual way: via binding of a macrocyclic ether to just one of the two available ruthenium ammine sites. We also report optical evidence for the onset of valence localization in both 1 and a trans pyridine (py) substituted analog (2), in the presence of either dibenzo-36-crown-12(DB-36-C-12) or dibenzo-30-crown-10 (DB-30-C-10) species. 17 refs., 3 figs.

• OSTI ID: 6297842
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:10; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
AROMATICS
CHARGED PARTICLES
CHEMICAL REACTIONS
COMPLEXES
ELECTRONIC STRUCTURE
ENCAPSULATION
ETHERS
HETEROCYCLIC OXYGEN COMPOUNDS
IONS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REDOX REACTIONS
RUTHENIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES