Synthetic routes to new polypyridyl complexes of osmium(II)
- Univ. of North Caroina, Chapel Hill (USA)
New luminescent complexes of Os(II) that contain either 2,2{prime}-bipyridine (bpy) or 1,10-phenanthroline (phen) as the chromophorib acceptor ligand have been prepared by a combination of established and new synthetic methods. Extensive use of Os(IV) and Os(III) precursors, e.g., Os{sup IV}(bpy)Cl{sub 4} and mer-Os{sup III}(PMe{sub 2}Ph){sub 3}Cl{sub 3} has led to the preparation of materials with ancillary ligands such as tertiary phosphines as preparative intermediates, including Os{sup III}(bpy)(PMe{sub 2}Ph)Cl{sub 3} and cis-Os{sup II}(phen)(diphosphine)Cl{sub 2}. Further substitution of chloro ligands into complexes such as these results in the formation of emissive complexes of Os(II). Another new synthetic route utilizes the versatile Os(II) precursor Os(bpy){sub 2}CO{sub 3}, which allows the facile preparation of dicationic, disubstituted species such as (Os(bpy){sub 2}(norbornadiene)){sup 2+}. Another general procedure, based on the control of solvent and temperature in the substitution chemistry of cis-Os(bpy){sub 2}Cl{sub 2}, has been further developed to produce a variety of new complexes of the types cis-(Os(bpy){sub 2}(L)Cl){sup +} and cis(Os(bpy){sub 2}(L){sub 2}){sup 2+}, where L is a phosphine, arsine, nitrogen, or olefin donor ligand. In a few cases, phosphine entering groups cause the cis geometry to be unfavorable and new trans-(Os(bpy){sub 2}(L){sub 2}){sup 2+} complexes have also been isolated. The resultant complexes comprise the largest family of transition-metal-based excited-state reagents with tunable photophysical and redox properties available. When possible, the new complexes have been characterized by UV-visible spectroscopy, emission spectroscopy, cyclic voltammetry, and {sup 31}P and/or {sup 1}H NMR spectroscopy.
- OSTI ID:
- 7108011
- Journal Information:
- Inorganic Chemistry; (USA), Vol. 27:25; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BIPYRIDINES
SYNTHESIS
OSMIUM COMPOUNDS
PHENANTHROLINES
LUMINESCENCE
NMR SPECTRA
PHOSPHORUS 31
PROTONS
AROMATICS
AZAARENES
AZINES
BARYONS
ELEMENTARY PARTICLES
FERMIONS
HADRONS
HETEROCYCLIC COMPOUNDS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUCLEONS
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS ISOTOPES
PYRIDINES
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation