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

Abstract

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).

Robust and highly emissive copper(i) halide 1D-coordination polymers with triphenylarsine and a series of bridging N-heteroaromatic co-ligands

“…4 Recently, CuX complexes with arsine ligands have piqued the attention of researchers for their structures and luminescence properties, even though phosphine and sulfides are the generally used complexes. 5 An arsenic atom has attractive properties for luminescent transition metal complexes. Because arsines are more air-stable than their corresponding phosphine analogs, an inert atmosphere is less necessary.…”

Noncovalent interactions in gold(iii) tetrakis(4-butoxyphenyl)porphyrinate structures

“…), and zero or very close to zero positive energy density in bond critical points (3, −1) for Au⋯Au, Au⋯Cl, and Au⋯O contacts in the crystal structures 1 , 1a , and 1b are typical for noncovalent interactions in similar chemical systems. 47–53 The estimated energies for these weak contacts in the crystal structures 1 , 1a , and 1b are 1.3–2.2 kcal mol −1 (Au⋯Au), 1.3–3.5 kcal mol −1 (Au⋯Cl), and 1.9–6.3 kcal mol −1 (Au⋯O). The balance between the Lagrangian kinetic energy G ( r ) and potential energy density V ( r ) at the bond critical points (3, −1) for Au⋯Au, Au⋯Cl, and Au⋯O contacts in the crystal structures 1 , 1a , and 1b ( viz.…”

From Mono- to Polynuclear 2-(Diphenylphosphino)pyridine-Based Cu(I) and Ag(I) Complexes: Synthesis, Structural Characterization, and DFT Calculations

“…Other possible modifications in the skeleton of the NP ligand involve the use of the corresponding phosphine oxides − or arsine derivatives. , In both cases, properties such as TADF and X-ray radioluminescence were detected in the derived Cu­(I) complexes.…”