Impact of High Pressure on Metallophilic Interactions and Its Consequences for Spectroscopic Properties of a Model Tetranuclear Silver(I)-Copper(I) Complex in the Solid State.

Structure-property relationships were investigated via combined high-pressure spectroscopic and X-ray diffraction techniques for a model luminescent Ag2Cu2L4 (L = 2-diphenylphosphino-3-methylindole) complex in the crystalline state. The experimental results were contributed by theoretical calculations, compared with the previously evaluated light-induced geometrical changes, and discussed in the context of available literature to date. To the best of our knowledge, this is the first study of this kind devoted to a coinage-metal complex for which the argentophilic interactions are crucial. High-pressure X-ray diffraction and optical spectroscopy experiments showed close correspondence between structural changes and optical properties. The unit-cell angles, absorption edges, emission maxima, decay lifetimes and silver-copper bond trends, all change around 2-3 GPa. A blue-shift to red-shift switch when increasing the pressure was observed for both absorption and emission spectra. This is unique behavior when compared to the literature-reported coinage metal systems. It also occurred that the pressure-induced structural changes differ notably from the geometrical distortions observed for the excited state. Interestingly, shortening of the Ag-Ag bond itself does not ensure the red shift of the absorption and emission spectra. All the optical spectroscopy data are suggestive of an important role of defects, likely related to the lack of a hydrostatic pressure transmitting medium, for pressures higher than 3 GPa.