Abstract
In this paper, we describe experimental evidence of a change in the emission energy as a function of the Au-Au distance. We have employed a luminescent complex exhibiting an aurophilic interaction, which is weak enough to allow its length to be modified by external pressure but rigid enough to confer structural stability on the complex. By determining the crystal structures and emission characteristics over a range of pressures, we have identified an exponential relationship between the energy of the emitted light and the metal-metal distances under pressure. This result can be indirectly related to the repulsive branch of the fitted function representing the energy of the system in the ground state at different Au-Au distances. The relativistic nature of gold appears to play an important role in the behavior of this complex.
Highlights
The pursuit of a direct relationship between weak interactions and emission wavelengths is not a new challenge
The diffraction experiment on the E-isomer enclosed in a diamond-anvil cell (DAC) at ambient pressure shows a crystal system, space group and unit cell dimensions different from those obtained previously,3 suggesting that a new phase of the E-isomer has been obtained (Table S1)
Since the main difference between the data collection at high pressure and at the original structural determination is the temperature at which the experiments were carried out, the effects of temperature on the E-isomer were investigated by means of variable-temperature experiment (See SI)
Summary
The pursuit of a direct relationship between weak interactions and emission wavelengths is not a new challenge. The preferred candidates to investigate it were square-planar Pt(II) and linear Au(I) closed-shell metal complexes, and more recently Ag(I) ones, because they usually display unsupported metal-metal interactions with a great variety of metal-metal distances, as has been summarized by Pyykkö, Schmidbaur et al in highly cited reviews.. The preferred candidates to investigate it were square-planar Pt(II) and linear Au(I) closed-shell metal complexes, and more recently Ag(I) ones, because they usually display unsupported metal-metal interactions with a great variety of metal-metal distances, as has been summarized by Pyykkö, Schmidbaur et al in highly cited reviews.1,2 This variety has even been found in the very unusual E/Z-isomerism between two isomers of complex [Au(C6Cl5)2Ag([9]aneS3)]2 recently reported by our laboratory.. In the case of the studies with different gold(I) salts, the different anions, cations or ligands produced conformational changes, which altered the molecular packing, or even changed the characters of emissions, leading to results which did not provide any insight.
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