Density functional calculations have been performed on titanium, nickel, molybdenum and niobium–Schiff base complexes and titanium, nickel–porphyrinogen complexes in order to understand the behavior of these systems in redox processes. In titanium and nickel–Schiff base complexes C–C sigma bonds are formed upon reduction, while in titanium and nickel–porphyrinogen complexes C–C sigma bonds are formed upon oxidation. In both systems, the formation or the cleavage of C–C bonds avoids a variation in the oxidation state of the metal and these C–C bonds act not only as electron reservoirs, but also as a buffer for the oxidation state of the metal. The possibility of intramolecular electron transfer from C–C bonds to M–M bonds and viceversa has been investigated for molybdenum and niobium–Schiff base complexes.
A theoretical approach to molecular batteries: C-C bonds functioning as electron shuttles
BELANZONI, Paola;ROSI, Marzio;SGAMELLOTTI, Antonio
2004
Abstract
Density functional calculations have been performed on titanium, nickel, molybdenum and niobium–Schiff base complexes and titanium, nickel–porphyrinogen complexes in order to understand the behavior of these systems in redox processes. In titanium and nickel–Schiff base complexes C–C sigma bonds are formed upon reduction, while in titanium and nickel–porphyrinogen complexes C–C sigma bonds are formed upon oxidation. In both systems, the formation or the cleavage of C–C bonds avoids a variation in the oxidation state of the metal and these C–C bonds act not only as electron reservoirs, but also as a buffer for the oxidation state of the metal. The possibility of intramolecular electron transfer from C–C bonds to M–M bonds and viceversa has been investigated for molybdenum and niobium–Schiff base complexes.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
