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基于羟基和羧基基团修饰的芳烃磺酸的新型银(I)配合物家族:合成、结构和发光性质。

New family of silver(I) complexes based on hydroxyl and carboxyl groups decorated arenesulfonic acid: syntheses, structures, and luminescent properties.

机构信息

Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China.

出版信息

Inorg Chem. 2011 Dec 19;50(24):12562-74. doi: 10.1021/ic201589p. Epub 2011 Nov 16.

DOI:10.1021/ic201589p
PMID:22087743
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) (3), [Ag(2)(HL2)(NH(3))(2)]·H(2)O (4), Ag(H(2)L2)(H(2)O) (5), Ag(2)(HL2) (6), Ag(3)(L3)(NH(3))(3) (7), Ag(2)(HL3) (8), and Ag(6)(L3)(2)(H(2)O)(3) (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.

摘要

自组装银(I)盐和三个邻位羟基和羧基基团修饰的芳基磺酸提供了形成九个银(I)-磺酸盐的机会,(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)和[Ag(6)(L3)(2)(H(2)O)(3)](n)(9)(H(3)L1 = 2-羟基-3-羧基-5-溴苯磺酸,H(3)L2 = 2-羟基-4-羧基苯磺酸,H(3)L3 = 2-羟基-5-羧基苯磺酸),这些都是通过元素分析、IR、TGA、PL 和单晶 X 射线衍射来表征的。复合物 1 是由[Ag(HL1)(NH(3))(H(2)O)](-)阴离子和 NH(4)(+)阳离子扩展的 3-D 超分子网络。复合物 2 表现出 3-D 主体-客体框架,其中封装了铵阳离子作为客体。复合物 3 呈现出由磺酸盐桥接的 Ag1 二聚体连接的[(Ag2)(2)(COO)(2)]双核单元构成的 2-D 层状结构。复合物 4 表现出 3-D 氢键主体-客体网络,其中封装了水分子作为客体。复合物 5 显示出由有机连接体桥接的 1-D Ag-O-S 链构成的 3-D 杂化骨架,而复合物 6 是具有由 Ag2 多面体链相互连接的 Ag1 二聚体和磺酸盐四面体构成的无机亚结构的 3-D 支柱层状框架。复合物 7 的混合 3-D 骨架由 L3(-)三阴离子桥接短三银(I)棒和银(I)链形成。复合物 8 也呈现出 3-D 支柱层状框架,无机层亚结构由磺酸盐四面体桥接[(Ag1O(4))(2)(Ag2O(5))(2)](∞)图案形成。复合物 9 代表了第一个含有四种配位球的基于银的金属多面体骨架,具有低配位数。结构的多样性和演变可归因于合成方法、三种功能基团的不同配体和配位模式,即磺酸盐、羟基和羧基。还研究了九个复合物的发光性质,特别是复合物 1 表现出优异的蓝色发光,并能敏化 Tb(III)离子以呈现特征的绿色发射。

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