Exploring the structural changes on excitation of a luminescent organic bromine-substituted complex by in-house time-resolved pump-probe diffraction

The structural changes accompanying the excitation of the luminescent dibromobenzene derivative, 1,4-dibromo-2,5-bis(octyloxy)benzene, have been measured by in-house monochromatic time-resolved (TR) diffraction at 90K. Results show an increment of the very short intermolecular Br·Br contact distance from 3.290Å to 3.380Å. Calculations show the BrBr interaction to be strongly repulsive in both the Ground and Excited states but significantly relaxed by the lengthening of the contact distance on excitation. The stability of the crystals is attributed to the many weak C-HBr and C-Hφ intermolecular interactions. The study described is the first practical application of In-House Time-Resolved diffraction, made possible by the continuing increase in the brightness of X-ray sources and the sensitivity of our detectors.