Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes

The coordination behavior of tris(2-pyridyl)arsine (Py₃As) has been studied for the first time on the example of the reactions with CuI, CuBr and AgClO₄. When treated with CuI in CH₂Cl₂ medium, Py₃As unexpectedly affords the scorpionate complex [Cu(Py₃As)I]∙CH₂Cl₂ only, while this reaction in MeCN selectively leads to the dimer [Cu₂(Py₃As)₂I₂]. At the same time, the interaction of CuBr with Py₃As exclusively gives the dimer [Cu₂(Py₃As)₂Br₂]. It is interesting to note that the scorpionate [Cu(Py₃As)I]∙CH₂Cl₂, upon fuming with a MeCN vapor (r.t., 1 h), undergoes quantitative dimerization into the dimer [Cu₂(Py₃As)₂I₂]. The reaction of Py₃As with AgClO₄ produces complex [Ag@Ag₄(Py₃As)₄](CIO₄)₅ featuring a Ag-centered Ag₄ tetrahedral kernel. At ambient temperature, the obtained Cu(I) complexes exhibit an unusually short-lived photoluminescence, which can be tentatively assigned to the thermally activated delayed fluorescence of (M + X) LCT type (M = Cu, L = Py₃As; X = halogen). For the title Ag(I) complexes, QTAIM calculations reveal the pronounced argentophilic interactions for all short Ag∙∙∙Ag contacts (3.209-3.313 Å).