Control of Electron Transfer Processes in Multidimensional Arylamine-Based Mixed-Valence Compounds by Molecular Backbone Design

2021 ◽  
Author(s):  
Agostina-L. Capodilupo ◽  
Eduardo Fabiano ◽  
Lorenzo Franco ◽  
Salvatore Gambino ◽  
Mauro Leoncini ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Mixed Valence ◽  
Transfer Processes ◽  
Molecular Backbone ◽  
Electron Transfer Processes ◽  
Mixed Valence Compounds

Crystal-Structures of Three Long, Rigid, Norbornylogous Compounds of Relevance to Distance-Dependence Studies of Long-Range Intramolecular Electron-Transfer Processes

1987 ◽  
Vol 40 (12) ◽  
pp. 1951 ◽  
Author(s):  
DC Craig ◽  
MN Paddonrow
Keyword(s):  
Electron Transfer ◽  
Crystal Structures ◽  
Dipole Moments ◽  
Intramolecular Electron Transfer ◽  
Time Resolved ◽  
Transfer Processes ◽  
Distance Dependence ◽  
Molecular Backbone ◽  
Predicted Values ◽  
Electron Transfer Processes

Results of previous studies revealed that photoinduced intramolecular electron transfer between the dimethoxynaphthalene donor and dicyanomethylene acceptor groups in the series of rigid alicyclic compounds (2a)-(6a) is extremely rapid. As the first step towards determining the distance dependence of the rate of photoinduced intramolecular electron transfer in these molecules, crystal structures of (3a), (4b) and (5b), have been measured. The edge-to-edge distance between the two chromophores in (3a), (4b) and (5b) is 6.8, 9.4, and 11.5 � respectively. The estimated centre-to-centre separation between the chromophores in (2a)-(6a) ranges from c. 7.1 � in (2a) to c. 14.9 � in (6a). From these results, dipole moments of the charge-separated states of (2a)-(6a), following photoinduced intramolecular electron transfer, could be estimated. These predicted values were in excellent agreement with those determined experimentally by using the time-resolved microwave conductivity technique. An interesting structural feature of (3a), (4b) and (5b) is the pronounced curvature of the molecular backbone in these molecules. It is predicted that approximately 24 linearly fused norbornyl and bicyclo[2.2.0] units would complete a circle, forming a member of a novel class of macrocycles, tentatively called dogcollaranes.

Switchable Electron-Transfer Processes in a Mixed-Valence, Kinetically Locked, Trinuclear RuII Metallamacrocycle

2004 ◽  
Vol 116 (30) ◽  
pp. 4028-4031 ◽  
Author(s):  
Naz Shan ◽  
Steven J. Vickers ◽  
Harry Adams ◽  
Michael D. Ward ◽  
Jim A. Thomas
Keyword(s):  
Electron Transfer ◽  
Mixed Valence ◽  
Transfer Processes ◽  
Electron Transfer Processes

Switchable Electron-Transfer Processes in a Mixed-Valence, Kinetically Locked, Trinuclear RuII Metallamacrocycle

2004 ◽  
Vol 43 (30) ◽  
pp. 3938-3941 ◽  
Author(s):  
Naz Shan ◽  
Steven J. Vickers ◽  
Harry Adams ◽  
Michael D. Ward ◽  
Jim A. Thomas
Keyword(s):  
Electron Transfer ◽  
Mixed Valence ◽  
Transfer Processes ◽  
Electron Transfer Processes

COMPUTATIONAL STUDY OF BRIDGE-MEDIATED INTERVALENCE ELECTRON TRANSFER II: COUPLINGS IN DIFFERENT METALLOCENE COMPLEXES

2012 ◽  
Vol 11 (06) ◽  
pp. 1341-1356 ◽  
Author(s):  
YINXI YU ◽  
HAOBIN WANG ◽  
SHAOWEI CHEN
Keyword(s):  
Electron Transfer ◽  
Density Functional ◽  
Computational Study ◽  
Mixed Valence ◽  
Functional Theory ◽  
Transfer Processes ◽  
Mediated Electron Transfer ◽  
Bridge Structures ◽  
Electron Transfer Processes ◽  
The Relationship

The constrained density functional theory (CDFT) was used to study bridge-mediated electron transfer processes in mixed-valence systems with two identical metallocene (cobaltocene, ruthenocene, and nickelocene) moieties linked by various bridge structures. Based on the electronic coupling matrix elements obtained from the CDFT calculations, the relationship between the bridge linkage and the effectiveness of intervalence transfer was discussed.

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