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

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

Journal

Molecules
, E-ISSN: 1420-3049

Output data

Year: 2022, Volume: 27, Number: 18, Pages: 6059 Pages count : 1 DOI: 10.3390/molecules27186059

Tags

tris(2-pyridyl)arsine; Cu(I) complexes; Ag(I) clusters; metallophilic interactions; thermally activated delayed fluorescence; dimerization

Authors

Demyanov Yan V. ¹ , Sadykov Evgeniy H. ¹ , Rakhmanova Marianna I. ¹ , Novikov Alexander S. ^2,3 , Bagryanskaya Irina Yu. ⁴ , Artem’ev Alexander V. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the RAS
2	Saint Petersburg State University
3	Peoples' Friendship University of Russia
4	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

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).

Demyanov Y.V. , Sadykov E.H. , Rakhmanova M.I. , Novikov A.S. , Bagryanskaya I.Y. , Artem’ev A.V.
Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes
Molecules. 2022. V.27. N18. P.6059. DOI: 10.3390/molecules27186059 WOS РИНЦ OpenAlex

Submitted:	Aug 23, 2022
Accepted:	Sep 8, 2022
Published online:	Sep 16, 2022

Web of science:	WOS:000858859400001
Elibrary:	59402279
OpenAlex:	W4296357998

DB	Citing
OpenAlex	14
Web of science	14