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New family of silver(I) complexes based on hydroxyl and carboxyl groups decorated arenesulfonic acid: syntheses, structures, and luminescent properties
Authors:Fang Xiang-Qian  Deng Zhao-Peng  Huo Li-Hua  Wan Wang  Zhu Zhi-Biao  Zhao Hui  Gao Shan
Institution:Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China.
Abstract:Self-assembly of silver(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords the formation of nine silver(I)-sulfonates, (NH(4))·Ag(HL1)(NH(3))(H(2)O)] (1), {(NH(4))·Ag(3)(HL1)(2)(NH(3))(H(2)O)]}(n) (2), Ag(2)(HL1)(H(2)O)(2)](n) (3), Ag(2)(HL2)(NH(3))(2)]·H(2)O (4), Ag(H(2)L2)(H(2)O)](n) (5), Ag(2)(HL2)](n) (6), Ag(3)(L3)(NH(3))(3)](n) (7), Ag(2)(HL3)](n) (8), and Ag(6)(L3)(2)(H(2)O)(3)](n) (9) (H(3)L1 = 2-hydroxyl-3-carboxyl-5-bromobenzenesulfonic acid, H(3)L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H(3)L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid), which are characterized by elemental analysis, IR, TGA, PL, and single-crystal X-ray diffraction. Complex 1 is 3-D supramolecular network extended by Ag(HL1)(NH(3))(H(2)O)](-) anions and NH(4)(+) cations. Complex 2 exhibits 3-D host-guest framework which encapsulates ammonium cations as guests. Complex 3 presents 2-D layer structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers linked by (Ag2)(2)(COO)(2)] binuclear units. Complex 4 exhibits 3-D hydrogen-bonding host-guest network which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged 1-D Ag-O-S chains while complex 6 is 3-D pillared layered framework with the inorganic substructure constructing from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate tetrahedra. The hybrid 3-D framework of complex 7 is formed by L3(-) trianions bridging short trisilver(I) sticks and silver(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic layer substructure is formed by the sulfonate tetrahedrons bridging (Ag1O(4))(2)(Ag2O(5))(2)](∞) motifs. Complex 9 represents the first silver-based metal-polyhedral framework containing four kinds of coordination spheres with low coordination numbers. The structural diversities and evolutions can be attributed to the synthetic methods, different ligands and coordination modes of the three functional groups, that is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties of the nine complexes have also been investigated at room temperature, especially, complex 1 presents excellent blue luminescence and can sensitize Tb(III) ion to exhibit characteristic green emission.
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