Spectroscopic properties and redox chemistry of the phosphorescent excited state of Pt/sub 2/(P/sub 2/O/sub 5/)/sub 4/H/sub 8//sup 4 -/

Journal Article · Tue Dec 29 23:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00416a021· OSTI ID:5225469

Che, C M; Butler, L G; Gray, H B

Binuclear complexes built from square-planar Rh(I) or Ir(I) isocyanide units exhibit rich photophysical and photochemical properties. Extensive studies in our laboratory have established that the lowest electronic excited states of one of these complexes, Rh/sub 2/b/sub 4//sup 2 +/ (b = 1.3-diisocyanopropane) (/sup 1/A/sub 1g/ (D/sub 4h/) ground state; Rh-Rh = 3.24 angstrom), are a spin triplet (/sup 3/A/sub 2u/) and a spin singlet (/sup 1/A/sub 2u/) derived from the dsigma/sup */psigma(1a/sub 2u/2a/sub 1g/) orbital configuration and that the E/sub u/(/sup 3/A/sub 2u/) phosphorescent state (t = 8.5 ..mu..s, CH/sub 3/CN solution, 25 /sup 0/C) undergoes electron-transfer reactions with donors and acceptors. Our decision to begin experiments with the goal of extending this type of photochemistry to analogous Pt(II) complexes was based mainly on reports of an intensely luminescent, phosphite-bridged binuclear species, Pt/sub 2/(P/sub 2/O/sub 5/)/sub 4/H/sub 8//sup 4 -/ (Pt-Pt = 2.93 angstrom). Our experiments have shown that the properties of the lowest electronic excited states of Pt/sub 2/(P/sub 2/0/sub 5/)/sub 4/H/sub 8//sup 4 -/ are entirely analogous to those of Rh/sub 2/b/sub 4//sup 2 -/, and they have provided the first examples of electron-transfer reactions involving excited Pt(II) species and acceptor molecules.

• Research Organization: California Inst. of Tech., Pasadena
• OSTI ID: 5225469
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:26; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200 -- Inorganic
Organic
& Physical Chemistry
400500* -- Photochemistry
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ELECTRON TRANSFER
EMISSION SPECTROSCOPY
ENERGY LEVELS
EQUATIONS
EXCITED STATES
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
INFORMATION
LUMINESCENCE
MEDIUM TEMPERATURE
NUMERICAL DATA
PHOSPHORESCENCE
PHOTOCHEMISTRY
PLATINUM COMPLEXES
QUENCHING
REDOX REACTIONS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES