A new copper(I) coordination polymer [Cu₆(μ₃-I)₆(μ₃-PTAO)₂]_n (1) was prepared from copper(I) iodide and 1,3,5-triaza-7-phosphaadamantane-7-oxide (PTAO). The crystal structure of 1 reveals an intricate 2D coordination network constructed from the hexacopper(I)-iodide [Cu₆(μ₃-I)₆] cluster units with the 4M6-1 topology interlinked by the μ₃-PTAO spacers. An overall 2D layer network can be simplified to a binodal 3,6-connected net with the kgd topology. A derived 1@paper material was prepared by impregnating compound 1 onto a filter paper. Detailed investigation of the luminescence properties for 1 and 1@paper in the solid state revealed a remarkable ability of both materials to sense aniline molecules in liquid and vapor phases at room temperature. The visibility to the naked eye and the reversible color response of 1 and 1@paper upon contact with aniline make these materials rather promising candidates for application as “turn-on” luminescence sensors for aniline recognition at room temperature. Visual aniline sensing detection limits of 0.26 and 0.065 ppb were observed for 1 and 1@paper under ambient conditions, respectively.

The new series of silver(I) coordination polymers [Ag(N–N)(μ-PTA)]_n(X)_n (1, 2, 4–8, 10, 11) and discrete monomers [Ag(N–N)(PTA)₂](X) (3, 9) {N–N = bpy (1–3), dtbpy (4), neocup (5, 6), phen (7–9), dione (10, 11); X = NO₃ (1, 3, 5, 7, 9, 10), PF₆ (2, 4, 6, 8, 11)} were generated by self-assembly reactions, in MeOH at ∼25 °C, of AgNO₃ or AgPF₆ with 1,3,5-triaza-7-phosphaadamantane (PTA) and the corresponding polypyridines, namely 2,2′-bipyridine (bpy), 4,4′-di-tert-butyl-2,2′-bipyridine (dtbpy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (neocup) and 1,10-phenanthroline-5,6-dione (dione). The compounds were obtained as air and light stable solids and characterized by IR, ¹H and ³¹P{¹H} NMR spectroscopy, ESI⁺-MS and elemental analyses. The crystal structure of 1 was determined by single crystal X-ray diffraction analysis, revealing infinite one-dimensional (1D) linear chains driven by μ-PTA N,P-linkers. Apart from representing the first examples of the metal–PTA derivatives bearing polypyridine ligands, 1–11 also feature solubility in water (S_25°C ≈ 4–18 mg mL⁻¹). Selected compounds (1, 3, 5, 7, 9 and 10) were thus tested for their biological properties and found to exhibit significant antibacterial and antifungal activities, screened in vitro against the standard strains of Staphylococcus aureus, Staphylococcus pyogenes, Staphylococcus pneumoniae, Staphylococcus sanguinis, Staphylococcus mutans, Enterococcus faecalis, Pseudomonas aeruginosa, Escherichia coli and Candida albicans. Furthermore, the compounds 5, 7, 9 and 10 show a pronounced antiproliferative activity against human malignant melanoma (A375), and the effects on the inhibition of tumor cells in vitro are in agreement with the DNA-binding studies.

Two new bioactive silver–organic frameworks [Ag(μ₃-PTAS)]_n(NO₃)_n·nH₂O (1) and [Ag₄(μ₄-PTAS)(μ₅-PTAS)(μ₂-SO₄)₂(H₂O)₂]_n·2nH₂O (2) were easily assembled, thus opening up the application of PTAS as a versatile N,S-building block in the crystal engineering of MOFs. The obtained products reveal infinite 3D networks driven by multiply bridging PTAS spacers that adopt unprecedented N₂S-coordination modes. The topological analysis of 1 discloses an uninodal 3-connected net with the srs (SrSi₂) topology, whereas 2 features a pentanodal 3,4,5-connected net with a hitherto undocumented topology. Apart from representing the first MOFs derived from PTAS, the compounds 1 and 2 display notable antibacterial and antifungal activities.