Solvothermal Synthesis of Four Polyoxometalate-Based Coordination Polymers Including Diverse Ag(I)···π Interactions

Abstract

Four 3D POM-based silver coordination polymers, namely, [Ag17(ptz)11(PW12O40)2]n (1), [Ag17(ptz)11(PMo12O40)2]n (2), [Ag12(ptz)6(CN)2(SiW12O40)]n (3), and [Ag19(ptz)8(H2ptz)(H3ptz)(AgP5W30O110)·7H2O]n (4), have been obtained by solvothermal reaction of AgNO3 and 5-phenyl-1H-tetrazole (Hptz) ligand in the presence of four types of polyoxometalates. Structural analysis shows that four types of Ag(I)···π interactions, m-η(1), m/p-η(2), o/m-η(2), and o/m/p-η(3), were observed in compounds 1-4, depending on the polyoxometalates used. The in situ generated CN(-) ion in compound 3 shows unprecedented mixed σ and π bonding modes, similar to the C2(2-) ion in well-studied silver acetylides. For 4, the Na(+) ion in the Preyssler heteropolyoxoanion, [NaP5W30O110](14-), was exchanged by Ag(I) under solvothermal conditions, generating a novel [AgP5W30O110](14-) anion. In addition, the photoluminescence behavior of 1-4 was also investigated.

Preyssler‐Pope‐Jeannin Polyanions [NaP5W30O110]14– and [AgP5W30O110]14–: Microwave‐Assisted Synthesis, Structure, and Biological Activity

“…This work also inspired others to investigate the host‐guest properties of {NaP 5 W 30 } . More recently, Ca 2+ , Bi 3+ , and even two K + ions have been encapsulated in this POM host, as well as Ag + …”

Cation Effect on Formation of Preyssler‐type 30‐Tungsto‐5‐phosphate: Enhanced Yield of Na‐encapsulated Derivative and Direct Synthesis of Ca‐ and Bi‐Encapsulated Derivatives

“…Therefore, the bond lengths between the encapsulated guest ion and oxygen atoms bridging two tungsten atoms decrease ( M –O b : 2.99–3.00 Å for Na + and Ag + , 2.89–2.90 Å for Ca 2+ , 2.59–2.67 Å for Y 3+ , Eu 3+ , and 2.59–2.67 Å for U 4+ ) with increasing charge of the guest ion, although the bond lengths between the encapsulated guest ion and the phosphate oxygen atoms remain almost constant (2.58–2.68 Å, see Table S1, Supporting Information). Interestingly, the distances between Bi 3+ and the oxygen atoms bridging two tungsten atoms are longer than those of Eu 3+ and Y 3+ , and in fact close to the distances of Na + or Ag + ,8a,9 and the distance between Bi 3+ and equatorial plane is shorter than that for Na + encapsulated molecule (Figure 7b and Table S1), which is probably due to the repulsion of the lone pair of electrons on Bi 3+ and the oxygen atoms bridging two tungsten atoms (O b ).…”

Assembly of three new POM-based Ag(I) coordination polymers with antibacterial and photocatalytic properties

“…To the date, some remarkable POMs-based polynuclear silver compounds constructed from rigid or flexible N-heterocycle ligands like imidazole, triazole, tetrazole and their derivatives have been synthesized and reported [16][17][18][19][20][21][22][23]. For example, Wang and her co-workers reported a new POM supported 2D silver-organic layer containing a molecular crown as a structural analog of calixarene [24].…”