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Coordination Versatility of Thiazolidinone-Based Ligands toward Ag + : Structural and Photophysical Insights
Julio Corredoira-Vázquez1,2, Manuel Saa3, Isabel García-Santos3
1Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela, Campus Vida, Santiago de Compostela 15782, Spain.
Abstract:
The reaction of the thiazolidinone-based ligands HAm4DHotaz, Am4Motaz, and Am4Eotaz with AgClO4 in a 1:1 molar ratio yields complexes of varying nuclearities depending on the Nthiazolidinone R-substituent. The unsubstituted HAm4DHotaz (R = H) affords the coordination polymer {[Ag-(HAm4DHotaz)]-(ClO4)} n (1) whereas Am4Motaz (R = Me) and Am4Eotaz (R = Et) lead to the discrete mononuclear complexes [Ag-(Am4Motaz)2]-(ClO4) (2) and [Ag-(Am4Eotaz)2]-(ClO4)] (3), respectively, as the main products. From the corresponding mother liquors, small amounts of the coordination polymers {[Ag-(Am4Motaz)-(ClO4)]} n (4) and {[Ag2(Am4Eotaz)2(H2O)-(ClO4)]-(ClO4)·H2O} n (5·H2O) were also obtained. In addition, the reaction of AgNO3 with Am4Eotaz in 1:1 or 0.5:1 molar ratio leads to [Ag-(Am4Motaz)2]-(NO3)·H2O (6·H2O), while the mother liquors of the 0.5:1 experiment produced small amounts of the coordination polymer {[Ag2(Am4Motaz)3]-(NO3)2·H2O} n (7·H2O). X-ray diffraction analyses of all the complexes highlight the remarkable coordination versatility of these ligands, revealing five distinct binding modes, including the unprecedented tridentate μ2-κ2NN':κ1N″ and μ2-κ1N:κ2N'S bridging motifs, as well as the two rarely reported modes μ2-κ2NN':κ1S and μ2-κ3NN'S:κ1. In addition, photophysical studies also highlight a pronounced dependence of the emission properties on the Nthiazolidinone R-substituent. Notably, although Ag+ coordination quenches ligand-centered emission in all cases, [Ag-(Am4Eotaz)2]-(ClO4)] (3) stands out as the only complex that remains emissive.
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