Photodegradation of Oligomeric Polyesters Containing Anthraquinone and 1,2-Diamine Units. Single Electron Transfer Induced Cation Radical Bond Cleavage in the Solid State

1995 ◽  
Vol 117 (8) ◽  
pp. 2226-2235 ◽  
Author(s):  
Jeffrey W. Leon ◽  
David G. Whitten
Keyword(s):  
Electron Transfer ◽  
Solid State ◽  
Bond Cleavage ◽  
Cation Radical ◽  
Single Electron ◽  
Single Electron Transfer

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

2002 ◽  
Vol 06 (07) ◽  
pp. 447-455
Author(s):  
Bin Yu ◽  
Yanxiu Zhou ◽  
Daike Wang ◽  
Zhenxing Wang ◽  
Kenichi Sugiura ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Cation Radical ◽  
Differential Pulse ◽  
Single Electron ◽  
Central Metal Atom ◽  
Central Metal ◽  
Single Electron Transfer ◽  
Electron Transfer Pathways ◽  
Chain Lengths

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H2OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu , Ni ), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a π-cation radical and reduced in three single-electron-transfer steps to yield a π-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

Reaction of Thianthrene Cation Radical with Diarylmercurials. Search for Single Electron Transfer Is Elusive

1993 ◽  
Vol 58 (1) ◽  
pp. 82-88 ◽  
Author(s):  
A. K. M. M. Hoque ◽  
Henry J. Shine ◽  
T. Krishnan Venkatachalam
Keyword(s):  
Electron Transfer ◽  
Cation Radical ◽  
Product Formation ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Aryl Radicals ◽  
Stoichiometric Ratios

Diarylmercurials (Ar2Hg) with Ar = p-tolyl Ib, o-tolyl Ic, p-anisyl Id and 2-allyloxy-4,5-dimethylphenyl Ie, reacted with thianthrene cation radical perchlorate (Th.+ClO4-) in two stoichiometric ratios: 2 : 1 and 4 : 1 (Th.+ClO4-/Ar2Hg). In the 2 : 1 ratio the products were the 5-arylthianthreniumyl perchlorates IIb - IIe, thianthrene (Th) and ArHg+ClO4- (assayed as ArHgCl, III) in quantitative yields. In the 4 : 1 ratio reaction with ArHg+ occurred, too, and the products were IIb - IIe, Th, the complex Th3Hg(ClO4)2 and HgO (after workup). In contrast, Ph2Hg (Ia) did not react beyond the 2 : 1 stoichiometry. In the reactions with Ie, no evidence for formation and cyclization of free 2-allyloxy-4,5-dimethylphenyl radical was found. Reaction of and product formation from these arylmercurials, therefore, does not occur in single electron transfer steps that lead to free aryl radicals. Instead electron transfer appears to occur within a complex of Ar2Hg with Th.+ from which II and other products are subsequently formed.

Sign in / Sign up

Export Citation Format

Share Document