Structural consequences of electron-transfer reactions. 10. Evidence for bending of a nitrosyl group during one-electron reduction of cyclopentadienyl metal nitrosyl compounds

1984 ◽  
Vol 106 (23) ◽  
pp. 7000-7006 ◽  
Author(s):  
William E. Geiger ◽  
Philip H. Rieger ◽  
Bunchai Tulyathan ◽  
Marvin D. Rausch
Keyword(s):  
Electron Transfer ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Metal Nitrosyl ◽  
Electron Reduction ◽  
Cyclopentadienyl Metal

Charge transfer emissive singlet excited states and photoinduced electron transfer properties in the diarylideneacetone compounds (RCHCH)2CO; R = phenyl, 1- and 2-naphthyl, 3-(N-ethylcarbazoyl), and 4-(C5H5)Fe(C5H4C6H4CHCH(CO)CHCHC6H5)

1990 ◽  
Vol 68 (12) ◽  
pp. 2278-2288 ◽  
Author(s):  
Pierre D. Harvey ◽  
Liangbing Gan ◽  
Christiane Aubry
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Charge Transfer ◽  
Excited States ◽  
Photoinduced Electron Transfer ◽  
Flash Photolysis ◽  
Reduction Process ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Electron Reduction

Four diarylideneacetone compounds ((RCHCH)2CO, where the aryl groups are phenyl (dba), 1-naphthyl (1-dNapha), 2-naphthyl (2-dNapha), and 3-(N-ethylcarbazoyl) (dNECa)), and 4-(C5H5)Fe(C5H4C6H4CHCH(CO)CHCH(C6H5) (dba-Fc) have been prepared and characterized. The compounds are found to be fluorescent and photochemically and reversibly electrochemically active. The lowest-energy absorption bands for the diarylideneacetones are assigned to a charge transfer (CT) electronic transition, except for dba-Fc, in which a ferrocenyl ligand field transition assignment is made. The 77 K CT absorption and fluorescence bands are vibrationally structured (vibrational spacings = 1260–1360 cm−1). While the fluorescence decay at 293 K is monoexponential, the excited state fluorescence lifetimes (τF) for the 77 K samples exhibit double exponential decays, the short component being 0.38–0.64 ns and the long one 3.5–10.9 ns. The photophysical results are interpreted in terms of excited state deactivation processes dominated by radiationless pathways that are associated with the presence of fluorescent species with different geometries. Only the dNECa compound is found to be fluorescent in solution at 298 K [Formula: see text]. Cyclic voltammetry and coulometry measurements suggest that a reversible one-electron reduction process and an irreversible higher potential one-electron reduction process take place in the −1 to −2 V vs. SSCE range. In addition, dba-Fc also exhibits an electrochemically reversible one-electron oxidation wave at 0.52 V vs. SSCE centered at the ferrocenyl group. These results together with the spectroscopic electronic data have permitted evaluation of the reduction potentials of the lowest singlet (CT excited states (E1−/*);they range from 1.4 to 2.2 V vs. SSCE, with dba being the strongest photooxidizing agent and dNECa the weakest. Photoinduced intermolecular electron transfer reactions have been investigated by steady state fluorescence techniques and picosecond flash photolysis spectroscopy for dNECa and dba, respectively. The bimolecular deactivation rate constants, kq, for the reductive photoinduced electron transfer reactions of dNECa with diphenylamine (DPA) (kq = (2.65 ± 0.25) × 107 M−1 s−1) and N, N, N′, N′-tetramethylphenylenediamine (TMPM) (kq = (1.38 ± 0.03) × 108 M−1 s−1) have been obtained in THF solutions at 293 K. No fluorescence quenching is observed when oxidative and energy transfer quenchers are used with dNECa. For the non-emissive dba compound at room temperature, picosecond flash photolysis experiments show that quenching of the broad dba transient band (~500 nm) does indeed occur between 5 and 10 ns. Keywords: dibenzylideneacetone, charge transfer, photoelectron transfer.

scholarly journals Single metal four-electron reduction by U(II) and masked “U(II)” compounds

2021 ◽  
Author(s):  
Marinella Mazzanti ◽  
Rosario Scopelliti ◽  
Maron Laurent ◽  
Iskander Douair ◽  
Chad Palumbo ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Redox Chemistry ◽  
Single Electron ◽  
Transfer Reactions ◽  
Single Electron Transfer ◽  
Electron Transfer Reactions ◽  
Element Chemistry ◽  
Electron Reduction ◽  
Electron Transfers

The redox chemistry of uranium is dominated by single electron transfer reactions while single metal four-electron transfers remain unknown in f-element chemistry. Here we show that the oxo bridged diuranium(III)...

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