ic8b01196_si_001.pdf (1.17 MB)
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
journal contribution
posted on 2018-07-03, 19:16 authored by Katarzyna N. Jarzembska, Radosław Kamiński, Kamil F. Dziubek, Margherita Citroni, Damian Paliwoda, Krzysztof Durka, Samuele Fanetti, Roberto BiniStructure–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.