Titov, A. A., Filippov, O. A., Smol’yakov, A. F., Godovikov, I. A., Shakirova, J. R., Tunik, S. P., Podkorytov, I. S. & Shubina, E. S. Luminescent Complexes of the Trinuclear Silver(I) and Copper(I) Pyrazolates Supported with Bis(diphenylphosphino)methane. Inorg. Chem. 58, 8645–8656 (2019).
DOI: 10.1021/acs.inorgchem.9b00991
The first example of trinuclear copper(I) and silver(I) pyrazolates adducts with a tertiary diphosphine (Ph2PCH2PPh2) retaining trimeric [MPz]3 core is reported. Despite rather strong M–P bonding, the complexes are able to undergo the dissociation of one M–P bond leading to the “merry-go-round” movement of P atoms over the M3 triangle. The copper complex displays emission from 1MLCT and 3MLCT states. The triplet and singlet states are separated by a relatively small energy gap (1080 cm–1) that triggers the thermally activated delayed fluorescence (TADF) behavior and leads to the worthy quantum yield of 41% at 298 K. The silver complex in the solid state and frozen solution shows dual emission originating from the 1IL and 3MLCT states that is dictated by the much higher energy difference between the emissive singlet and triplet as well as by the essentially different nature of these states.
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