On the elusive, non-emissive yet reactive, upper excited states of [(4,4′-bpy)Re(CO)3(dppz)]PF6 (dppz = dipyridil[3,2-a:2′3′-c]phenazine) |
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Authors: | GT Ruiz E Wolcan |
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Institution: | a INIFTA, Universidad Nacional de La Plata, C.C. 16, Suc. 4, 1900 La Plata, Argentina b Radiation Research Building, Department of Chemistry, University of Notre Dame, Notre Dame, IN 46556, USA |
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Abstract: | Gradual solvation of (4,4′-bpy)ReI(CO)3(dppz)]+ (dppz = dipyridil3,2-a:2′3′-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 ?, is therefore very close to the distance from the Re center to the oxygen atom of the CO ligands, i.e., l = 2.73 ?. In addition, excited state reactions with TEA produce (4,4′-bpy −)ReI(CO)3(dppz)] and (4,4′-bpy)ReI(CO)3(dppz −)]. This experimental observation is inconsistent with the formation of the products in the lowest lying and emissive dppz-centered 3ππ* excited state. Jablonski schemes based on the participation of excited states other than the lowest 3ππ* excited state are proposed. |
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Keywords: | Triscarbonylrhenium(I) dppz Reactive excited state Electron-transfer quenching |
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