Syntheses, Structures, and Luminescent Properties of Silver(I) Complexes Constructed from ortho-Hydroxyl Arenesulfonic Acids

Eight novel silver(I) complexes constructed from ortho-hydroxyl arene-sulfonic acids, [Ag(NH3)(2)] center dot (HL1) (1), [Ag-2(L1)](n) (2), [Ag-2(HL2)(H2O)(3)](n) (3), [Ag(HL3)(MeCN)(2)](n) (4), [Ag-2(HL3)(2)](n) (5), [Ag-2(HL4)(H2O)(3)](n) (6), {(NH4)(2) center dot - [Ag(NH3)(2)](2)} center dot 2(H2L5) center dot 5H(2)O (7), and [Ag(H(2)L5)(0.5)](n) (8) (H(2)L1 = 2-hydroxyl-5-methyl-benzenesulfonic acid; H(3)L2 = 2-hydroxyl-5-methyl-1,3-benzenedisulfonic acid; H(2)L3 = 2-hydroxyl-5-bromo-benzenesulfonic acid; H(3)L4 = 2-hydroxyl-5-bromo-1,3-benzenedisulfonic acid; H(4)L5 = 2,4-dihydroxyl-1,5-benzenedisulfonic acid), have been synthesized and characterized by elemental analysis, infrared, thermogravimetric analysis, UV-vis, photoluminescence (PL), powder and single-crystal X-ray diffraction. Complex 1 has a three-dimensional (3-D) supramolecular framework containing right-handed helical channels through the hydrogen-bonding interactions. Complex 2 exhibits a wavelike inorgano-organic layer structure, in which the inorganic substructures consist of Ag1 polyhedral chains linked through Ag2 dimers by sharing two vertexes and two edges. Complex 3 presents the 3-D pillared layered structure, and the inorganic layer substructures are formed by sulfonate tetrahedra bridging Ag-O chains through two vertexes. The sulfonate group in complex 4 bridges adjacent Ag(I) ions to generate a one-dimensional chain structure. Complex 5 exhibits a planar inorgano-organic layer structure, in which the inorganic substructures consist of chains of vertex-sharing Ag1 polyhedra and edge-sharing Ag2 polyhedra interlinked by sharing edges. Complex 6 shows a similar 3-D pillared layered structure with complex 3. In complex 7, the free water molecules, ammonium cations, and sulfonate groups form a 3-D hydrogen-bonding host network which encapsulates the [Ag(NH3)(2)](+) cations as guests. Complex 8 also displays a 3-D pillared layered structure with a two-dimensional (2-D) inorganic substructure formed by Ag(I) polyhedral chains interlinked by sharing edges. The structural diversities and evolutions can be attributed to the different ligands and the coordination modes of the sulfonate groups which are influenced by the hydroxyl groups. The solid-state luminescent properties have also been investigated at room temperature.