Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes
oleh: Yan V. Demyanov, Evgeniy H. Sadykov, Marianna I. Rakhmanova, Alexander S. Novikov, Irina Yu. Bagryanskaya, Alexander V. Artem’ev
| Format: | Article |
|---|---|
| Diterbitkan: | MDPI AG 2022-09-01 |
Deskripsi
The coordination behavior of tris(2-pyridyl)arsine (Py<sub>3</sub>As) has been studied for the first time on the example of the reactions with CuI, CuBr and AgClO<sub>4</sub>. When treated with CuI in CH<sub>2</sub>Cl<sub>2</sub> medium, Py<sub>3</sub>As unexpectedly affords the scorpionate complex [Cu(Py<sub>3</sub>As)I]∙CH<sub>2</sub>Cl<sub>2</sub> only, while this reaction in MeCN selectively leads to the dimer [Cu<sub>2</sub>(Py<sub>3</sub>As)<sub>2</sub>I<sub>2</sub>]. At the same time, the interaction of CuBr with Py<sub>3</sub>As exclusively gives the dimer [Cu<sub>2</sub>(Py<sub>3</sub>As)<sub>2</sub>Br<sub>2</sub>]. It is interesting to note that the scorpionate [Cu(Py<sub>3</sub>As)I]∙CH<sub>2</sub>Cl<sub>2</sub>, upon fuming with a MeCN vapor (r.t., 1 h), undergoes quantitative dimerization into the dimer [Cu<sub>2</sub>(Py<sub>3</sub>As)<sub>2</sub>I<sub>2</sub>]. The reaction of Py<sub>3</sub>As with AgClO<sub>4</sub> produces complex [Ag@Ag<sub>4</sub>(Py<sub>3</sub>As)<sub>4</sub>](CIO<sub>4</sub>)<sub>5</sub> featuring a Ag-centered Ag<sub>4</sub> 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 = Py<sub>3</sub>As; 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).