The development of Laue techniques for single-pulse diffraction of chemical complexes: time-resolved Laue diffraction...

A modified Laue method is shown to produce excited-state structures at atomic resolution of a quality competitive with those from monochromatic experiments. The much faster data collection allows the use of only one or a few X-ray pulses per data frame, which minimizes crystal damage caused by laser exposure of the samples and optimizes the attainable time resolution. The method has been applied to crystals of the α-modification of Rh(2)(μ-PNP)(2)(PNP)(2) (BPh(4))(2) [PNP = CH(3)N(P(OCH(3))(2))(2), Ph = phenyl]. The experimental results show a shortening of the Rh-Rh distance in the organometallic complex of 0.136 (8) Å on excitation and are quantitatively supported by quantum-mechanical (QM)/molecular-mechanics (MM) theoretical calculations which take into account the confining effect of the crystal environment, but not by theoretical results on the isolated complex, demonstrating the defining effect of the crystal matrix.