Dynamics of Photoinduced Intramolecular and Intermolecular Electron Transfers in Ligand-Conjugated Ir(III)-Re(I) Photocatalysts

초록

We report the electron transfer (ET) dynamics in a series of Ir(III)-Re(I) photocatalysts where two bipyridyl ligands of Ir and Re moieties are conjugated at the meta (m)-or para (p)-position of each side. Femtosecond transient absorption (TA) measurements identify the intramolecular ET (IET) dynamics from the Ir to Re moiety, followed by the formation of one-electron-reduced species (OERS) via the intermolecular ET with a sacrificial electron donor (SED). The IET rate depends on the bridging ligand (BL) structures (similar to 25 ps for BLmm/mp vs similar to 68 ps for BLpm/pp), while the OERS formation happens on an even slower time scale (similar to 1.4 ns). Connecting the Re moiety at the meta-position of the bipyridyl of the Ir moiety can restrict the rotation around a covalent bond between two bipyridyl ligands by steric hindrances and facilitate the IET process. This highlights the importance of BL structures on the ET dynamics in photocatalysts.

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