1D and 2D silver-based coordination polymers with thiomorpholine-4-carbonitrile and aromatic polyoxoacids as co-ligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study

Predrag Ristić , Tamara Todorovic , Vladimir Blagojević , Olivera Klisuric , Ivana Marjanović , Berta Holló , Predrag Vulic , Mihaela Gulea (1) , Morgan Donnard (2) , Miguel Monge , María Rodríguez-Castillo , José Lopez-De-Luzuriaga , Nenad Filipovic

1 LIT - Laboratoire d'Innovation Thérapeutique
2 LIMA - Laboratoire d'innovation moléculaire et applications

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036–0.056 min–1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet–singlet electronic excitations to the fluorescence, indicating that metal– intraligand transitions are responsible for luminescence in both complexes.

Mots clés: Silver complexes; Coordination polymers; Intermolecular interactions; Photoluminescence; Photocatalysis; TD-DFT

Domaines: Chimie organique

Predrag Ristić, Tamara Todorovic, Vladimir Blagojević, Olivera Klisuric, Ivana Marjanović, et al.. 1D and 2D silver-based coordination polymers with thiomorpholine-4-carbonitrile and aromatic polyoxoacids as co-ligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study. Crystal Growth & Design, 2020, 20 (7), pp.4461-4478. ⟨10.1021/acs.cgd.0c00287⟩. ⟨hal-02917283⟩