Excited state molecular structure determination in disordered media using laser pump/X-ray probe time-domain X-ray absorption spectroscopy

Abstract

Advances in X-ray technologies provide opportunities for solving structures of photoexcited state molecules with short lifetimes. Using X-ray pulses from a modern synchrotron source, the structure of a metal-to-ligand-charge-transfer (MLCT) excited state of Cu^I(dmp)₂⁺ (dmp = 2,9-dimethyl-1,10-phenanthroline) was investigated by laser pump/X-ray probe X-ray absorption fine structure (LPXP-XAFS) in fluid solution at room temperature on a nanosecond time scale. The experimental requirements for such pump–probe XAFS are described in terms of technical challenges: (1) conversion of optimal excited state population, (2) synchronization of the pump laser pulse and probe X-ray pulse, and (3) timing of the detection. Using a laser pump pulse for the photoexcitation, a photoluminescent MLCT excited state of Cu^I(dmp)₂(BArF), (dmp = 2,9-dimethyl-1,10-phenanthroline, BArF = tetrakis(3,5-bis(trifluoromethylphenyl)borate) with a lifetime of 98 ± 5 ns was created. Probing the structure of this state at its optimal concentration using an X-ray pulse cluster with a total duration of 14.2 ns revealed that (1) a Cu^II center was generated via a whole charge transfer; (2) the copper in the MLCT state bound an additional ligand to form a penta-coordinate complex with a likely trigonal bipyramidal geometry; and (3) the average Cu–N bond length increases in the MLCT excited state by 0.07 Å. In contrast to previously reported literature, the photoluminescence of this penta-coordinate MLCT state was not quenched upon ligation with the fifth ligand. On the basis of experimental results, we propose that the absorptive and emissive states have distinct geometries. The results represent X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.