Synthesis and characterizations of cyclometalated iridium(III) solvento complexes
Journal Article
·
· Inorganic Chemistry; (United States)
- Univ. of California, Santa Barbara, CA (United States)
Complexes of the type [Ir(L)[sub 2](S)[sub 2]][OTf] have been prepared by reactions of [Ir(L)[sub 2]Cl][sub 2] with AgOTf in an appropriate solvent medium (L = 2-phenylpyridine (ppy) or 2-(p-tolyl)pyridine (ptpy); S = H[sub 2]O or CH[sub 3]CN; OTf = CF[sub 3]SO[sub 3][sup [minus]]). These solvento complexes have been characterized by [sup 1]H and [sup 13]C NMR spectroscopies, UV-visible absorption and emission spectroscopies, and cyclic voltammetry. Estimates of radiative lifetimes based upon weak integrated absorption bands in the 460-490 nm region are in agreement with emission lifetimes monitored in glasses at 77 K. Low-lying excited states responsible for these absorption and emission bands are assigned to an admixture of ligand-localized and metal-to-ligand charge-transfer character. Quenching of the emissions in ambient solutions is discussed in terms of ligand labilization due to either thermal population of metal-centered excited states or direct labilization in the MLCT excited state due to enhanced trans effects of the Ir-C bonds on the Ir-S bonding.
- DOE Contract Number:
- FG03-88ER13842
- OSTI ID:
- 5035789
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 33:1; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400400 -- Electrochemistry
400500 -- Photochemistry
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
AZINES
CARBON 13
CARBON ISOTOPES
CHEMICAL PREPARATION
COMPLEXES
ELECTRONIC STRUCTURE
EMISSION SPECTROSCOPY
EVEN-ODD NUCLEI
HETEROCYCLIC COMPOUNDS
IRIDIUM COMPLEXES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
RESONANCE
SOLVENTS
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
400201* -- Chemical & Physicochemical Properties
400400 -- Electrochemistry
400500 -- Photochemistry
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
AZINES
CARBON 13
CARBON ISOTOPES
CHEMICAL PREPARATION
COMPLEXES
ELECTRONIC STRUCTURE
EMISSION SPECTROSCOPY
EVEN-ODD NUCLEI
HETEROCYCLIC COMPOUNDS
IRIDIUM COMPLEXES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
RESONANCE
SOLVENTS
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY