On the elusive, non emissive yet reactive, upper excited states of [(4,4'-bpy)ReI(CO)3(dppz)]PF6 (dppz = dipyridil[3,2-a:2’3’-c]phenazine)

G.T. RUIZ; G. FERRAUDI; E. WOLCAN; M.R. FÉLIZ

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Año: 2010 vol. 363 p. 1615 - 1618

0020-1693

Gradual solvation of [(4,40-bpy)ReI(CO)3(dppz)]+ (dppz = dipyridil[3,2-a:2030-c]phenazine) by water molecules causes a quenching of the emission in accordance with Perrin’s model of spheres. The calculated radius of the sphere, r = 2.6 ± 0.2 ÅA 0 causes a quenching of the emission in accordance with Perrin’s model of spheres. The calculated radius of the sphere, r = 2.6 ± 0.2 ÅA 0 0-bpy)ReI(CO)3(dppz)]+ (dppz = dipyridil[3,2-a:2030-c]phenazine) by water molecules causes a quenching of the emission in accordance with Perrin’s model of spheres. The calculated radius of the sphere, r = 2.6 ± 0.2 ÅA 0r = 2.6 ± 0.2 ÅA 0 , is therefore very close to the distance from the Re center to the oxygen atom of the CO ligands, i.e., l = 2.73 ÅA 0l = 2.73 ÅA 0 . In addition, excited state reactions with TEA produce [(4,40- bpyÆ)ReI(CO)3(dppz)] and [(4,40-bpy)ReI(CO)3(dppzÆ)]. This experimental observation is inconsistent with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. bpyÆ)ReI(CO)3(dppz)] and [(4,40-bpy)ReI(CO)3(dppzÆ)]. This experimental observation is inconsistent with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. 0- bpyÆ)ReI(CO)3(dppz)] and [(4,40-bpy)ReI(CO)3(dppzÆ)]. This experimental observation is inconsistent with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Æ)ReI(CO)3(dppz)] and [(4,40-bpy)ReI(CO)3(dppzÆ)]. This experimental observation is inconsistent with the formation of the products in the lowest lying and emissive dppz-centered 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. 3pp* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3pp* excited state are proposed. are proposed. 3pp* excited state are proposed.