1D and 2D Silver-Based Coordination Polymers with Thiomorpholine-4-carbonitrile and Aromatic Polyoxoacids as Coligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study

Abstract

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.

Leaching Kinetics of Hemimorphite with 5-Sulfosalicylic Acid

“…5-sulfosalicylic acid belongs to the family of aryloxyacids [21][22][23]. It is highly soluble in water, enabling its use in many applications [24]. In particular, sulfosalicylic acid is an important complexing agent.…”

Two Isomers of a Novel Ag(I) Complex with Pyrazole-Type Ligand—Synthesis, Structural, Thermal, and Antioxidative Characterization

“…Silver(I) compounds are known as good antimicrobial agents [7,14]. The Ag(I) ion can also form coordination polymers with photocatalytic and photoluminescent properties [15,16]. In complex compounds, Ag(I) is often bicoordinated, but in coordination polymers, it forms three or four coordinative bonds.…”

Polymeric Copper(II) Complexes with a Newly Synthesized Biphenyldicarboxylic Acid Schiff Base Ligand—Synthesis, Structural and Thermal Characterization

“…In recent years, coordination polymers (CPs) have become the focus of attention of numerous research groups because of their structural characteristics and topologies, as well as their various applications. The most important fields of potential applications are catalysis [1,2], luminescence [3], magnetism [4,5], gas storage [6], adsorption [7,8], etc. A great majority of the synthesized and characterized CPs contain dand f -metals such as Ag, Zn, Cd, Fe, Mn, Cu, and lanthanides.…”