Exciplex formation of copper(II) octaethylporphyrin revealed by pulsed X-rays

The triplet excited structures of Cu(II) octaethylporphyrin (CuOEP) in toluene and in 1:1 mixture of toluene and tetrahydrofuran (THF) were investigated by time-domain laser pulse pump, X-ray pulse probe X-ray absorption spectroscopy (pump-probe XAS) at room temperature using X-rays from a third generation synchrotron source with 100-ps time resolution. The transient optical absorption measurements indicate a strong solvent dependency of the triplet excited state lifetime due to the presence of oxygen-containing solvent molecules. While the ground state CuOEP molecules remain square-planar in both solvents, the attenuation of a peak attributed to the 1s→4p _z transition at the Cu K-edge for the laser excited CuOEP in the THF/toluene mixture revealed the penta-coordinated exciplex formation which is responsible for the shortening of the triplet excited state lifetime. Meanwhile, the average Cu-N distance in the triplet excited state is lengthened by 0.03 Å due to ligation with a THF solvent molecule, which agrees with a domed coordination structure for copper in the penta-coordinated exciplex.