Heteronuclear Gold(I)-Copper(I) Complexes with Thia- and Mixed Thia-Aza Macrocyclic Ligands: Synthesis, Structures and Optical Properties.

Autor: Donamaría R; Departamento de Química, Instituto de Investigación en Química (IQUR), Complejo Científico Tecnológico, Universidad de La Rioja, Madre de Dios 53, 26004, Logroño, Spain., Lippolis V; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042, Monserrato, CA, Italy., López-de-Luzuriaga JM; Departamento de Química, Instituto de Investigación en Química (IQUR), Complejo Científico Tecnológico, Universidad de La Rioja, Madre de Dios 53, 26004, Logroño, Spain., Monge M; Departamento de Química, Instituto de Investigación en Química (IQUR), Complejo Científico Tecnológico, Universidad de La Rioja, Madre de Dios 53, 26004, Logroño, Spain., Olmos ME; Departamento de Química, Instituto de Investigación en Química (IQUR), Complejo Científico Tecnológico, Universidad de La Rioja, Madre de Dios 53, 26004, Logroño, Spain.
Jazyk: angličtina
Zdroj: ChemPlusChem [Chempluschem] 2024 Mar; Vol. 89 (3), pp. e202300429. Date of Electronic Publication: 2023 Dec 05.
DOI: 10.1002/cplu.202300429
Abstrakt: The reactivity of the heterometallic polynuclear complexes [{Au(R) 2 } 2 Cu 2 (MeCN) 2 ] n (R=C 6 F 5 , C 6 Cl 5 ) with the thioether crowns 1,4,7-trithiacyclononane (L1, [12]aneS 3 ), 1,4,8,11-tetrathiacyclododecane (L2, [14]aneS 4 ), 1,4,7,10,13,16,19,22-octathiacyclotetracosane (L3, [24]aneS 8 ), and the quinoline functionalized pendant arm derivatives of the 12-membered mixed-donor macrocycles 1-aza-,4,7,10-trithiacyclododecane ([12]aneNS 3 ) and 1,7-diaza-4,10-dithiacyclododecane ([12]aneN 2 S 2 ), L4 and L5, respectively, was investigated in THF solution. While with L4 and L5 only ionic compounds of general formulation [Cu(L)][Au(R) 2 ] were isolated and structurally characterized (none of them featuring Au⋅⋅⋅Cu interactions), with L1-L3, beside similar ionic compounds, some heteronuclear complexes of general formulation [{Au(R) 2 }{Cu(L)}] and featuring Au⋅⋅⋅Cu interactions were also obtained. All of them display rather unusual non-classical C-H⋅⋅⋅Au hydrogen interactions. The complexes display in the solid state different optical properties related to their structures, which have been studied experimentally and theoretically via TD-DFT calculations. In particular, all compounds of the type [{Au(R) 2 }{Cu(L)}] featuring Au⋅⋅⋅Cu metallophilic interactions display luminescence in the solid state both at room temperature (RT) and at 77 K. On the contrary, ionic compounds of general formulation [Cu(L)][Au(R) 2 ], except [Cu(L4)][Au(C 6 F 5 ) 2 ], are not luminescent.
(© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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