Description
Title: A New Design Platform for Luminescent Cu(I) and Ag(I) Complexes Using Tris(2-Pyridyl)Arsine
Abstract: Tris(2-pyridyl)arsine (Py3As) coordination behavior has been studied for the first time using the examples of reactions with CuI, CuBr, and AgClO4. Py3As unexpectedly produces the scorpionate complex [Cu(Py3As)I]CH2Cl2 only when treated with CuI in CH2Cl2 medium, whereas this reaction in MeCN only produces the dimer [Cu2(Py3As)2I2]. At the same time, the dimer [Cu2(Py3As)2Br2] is the only product of CuBr’s interaction with Py3As. It’s interesting to note that the scorpionate [Cu(Py3As)I]CH2Cl2 undergoes quantitative dimerization into the dimer [Cu2(Py3As)2I2] after fuming with a MeCN vapor for one hour. Py3As reacts with AgClO4 to form the complex [Ag@Ag4(Py3As)4](CIO4)5, which has an Ag4 tetrahedral kernel at its center. The obtained Cu(I) complexes display an abnormally brief photoluminescence at room temperature, which can be tentatively attributed to the thermally activated delayed fluorescence of the (M + X) LCT type (M = Cu, L = Py3As; X = halogen). QTAIM calculations show the pronounced argentophilic interactions for all short AgAg contacts (3.209-3.313 ) for the title Ag(I) complexes.
Keywords: tris(2-pyridyl)arsine; Cu(I) complexes; Ag(I) clusters; metallophilic interactions; thermally activated delayed fluorescence; dimerization
Paper Quality: SCOPUS / Web of Science Level Research Paper
Subject: Chemistry
Writer Experience: 20+ Years
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