Synthetic control of excited states. Nonchromophoric ligand variations in polypyridyl complexes of osmium(II)

Journal Article · Wed Aug 28 00:00:00 EDT 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00212a010· OSTI ID:5104224

Kober, E M; Marshall, J L; Dressick, W J; Sullivan, B P; Caspar, J V; Meyer, T J

Two themes are explored with regard to the properties of the metal to ligand charge-transfer (MLCT) excited states of Os(II). For a series of Os(II) complexes it is shown that the MLCT excited states undergo facile oxidative or reductive quenching. Excited-state redox potentials have been estimated by both kinetic quenching and spectroscopic techniques for excited-state oxidative couples and excited-state reductive couples. The second theme, the manipulation of excited-state properties by synthetic changes, follows from a consideration of these factors that dictate excited-state redox potentials. It is shown that in the series (phen)OsL/sub 4//sup 2 +/ (L = pyridine, CH/sub 3/CN, PR/sub 3/, AsR/sub 3/, ... and phen = 1,10-phenanthroline) where the metal-ligand basis for the MLCT chromophore remains the same and variations are made in the nonchromophoric ligand, emission energies, excited-state redox potentials, and radiative and nonradiative rate constants all vary systematically with the potential of the ground-state Os(III/II) couple. The results show that it is possible through synthetic changes to control excited-state properties in a systematical way. 37 references, 6 figures, 5 tables.

• Research Organization: Univ. of North Carolina, Chapel Hill
• DOE Contract Number: AS05-78ER06034
• OSTI ID: 5104224
• Journal Information: Inorg. Chem.; (United States), Vol. 24:18
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
FLUORESCENCE
RADIATIONLESS DECAY
REDOX POTENTIAL
ARSENIC
CYANIDES
OSMIUM COMPLEXES
PHENANTHROLINES
PHOSPHORUS
PYRIDINES
CHARGE TRANSPORT
EXCITED STATES
EXPERIMENTAL DATA
GROUND STATES
LIGANDS
OSMIUM
AROMATICS
AZAARENES
AZINES
COMPLEXES
DATA
DE-EXCITATION
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
LUMINESCENCE
METALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PLATINUM METALS
SEMIMETALS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)