Slow intramolecular electron transfer in a ruthenium(III)-titanium(III) redox intermediate having a dianion derived from a dihydroxyquinone as bridging ligand

1993 ◽  
Vol 32 (2) ◽  
pp. 189-193 ◽  
Author(s):  
Kejian Lu ◽  
Joseph E. Earley
Keyword(s):  
Electron Transfer ◽  
Intramolecular Electron Transfer ◽  
Bridging Ligand

scholarly journals Which bridge to cross, which mountain to climb – Supramolecular Photocatalysis Outpacing Conventional Catalysis

2021 ◽  
Author(s):  
Linda Zedler ◽  
Pascal Wintergerst ◽  
Alexander Mengele ◽  
Carolin Müller ◽  
Chunyu Li ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photocatalytic Activity ◽  
Intramolecular Electron Transfer ◽  
Design Strategies ◽  
Electron Transfer Kinetics ◽  
Tert Butyl ◽  
Bridging Ligand ◽  
The One ◽  
Rate Limiting

Unequivocal assignment of rate limiting steps in supramolecular photocatalysts is of utmost importance to rationally optimize photocatalytic activity. By spectroscopic and catalytic analysis of a series of three structurally similar [(tbbpy) 2 Ru-BL-Rh(Cp*)Cl] 3+ photocatalysts just differing in the central part (alkynyl, triazole or phenazine) of the bridging ligand (BL) we were able to derive design strategies for improved photocatalytic activity of this class of compounds (tbbpy = 4,4´-tert-butyl- 2,2´-bipyridine, Cp* = pentamethylcyclopentadienyl). Most importantly, not the rate of the transfer of the first electron towards the Rh III center but rather the rate at which a two-fold reduced Rh I species is generated can directly be correlated with the observed photocatalytic formation of NADH from NAD + . Interestingly, the complex which exhibited the fastest intramolecular electron transfer kinetics for the first electron is not the one that allowed the fastest photocatalysis. With the photocatalytically most efficient alkynyl linked system, it was even possible to overcome the rate of thermal NADH formation. Moreover, for this photocatalyst loss of the alkynyl functionality under photocatalytic conditions was identified as an important deactivation pathway.

Intramolecular Electron Transfer Mediated by a Tetrathiafulvalene Bridge in a Purely Organic Mixed-Valence System

2003 ◽  
Vol 42 (24) ◽  
pp. 2765-2768 ◽  
Author(s):  
Nicolas Gautier ◽  
Frédéric Dumur ◽  
Vega Lloveras ◽  
José Vidal-Gancedo ◽  
Jaume Veciana ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Mixed Valence ◽  
Intramolecular Electron Transfer

scholarly journals Solvent-induced on/off switching of intramolecular electron transfer in a cyanide-bridged trigonal bipyramidal complex

2016 ◽  
Vol 45 (43) ◽  
pp. 17104-17107 ◽  
Author(s):  
Rong-Jia Wei ◽  
Ryohei Nakahara ◽  
Jamie M. Cameron ◽  
Graham N. Newton ◽  
Takuya Shiga ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Spin Transition ◽  
Intramolecular Electron Transfer ◽  
Thermally Induced ◽  
Trigonal Bipyramidal ◽  
Transition Behaviour

A cyanide-bridged trigonal bipyramidal [Co3Fe2] cluster shows solvent-driven reversible on/off switching of its thermally induced electron-transfer-coupled spin transition behaviour.

Sign in / Sign up

Export Citation Format

Share Document