Anion-dependent self-assembly of silver(I) and diaminotriazines to coordination polymers: non-covalent bonds and role interchange between silver and hydrogen bonds.
Anion-dependent self-assembly of silver(I) and diaminotriazines to coordination polymers: non-covalent bonds and role interchange between silver and hydrogen bonds.
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DOI：
10.1021/ic800997d
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发表时间：
2008-09
影响因子：
4.6
通讯作者：
B. Manzano;F. A. Jalón;M. Laura Soriano;M. C. Carrión;M. P. Carranza;K. Mereiter;A. M. Rodríguez;A. de la Hoz;A. Sánchez-Migallón
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文献类型：
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作者：
B. Manzano;F. A. Jalón;M. Laura Soriano;M. C. Carrión;M. P. Carranza;K. Mereiter;A. M. Rodríguez;A. de la Hoz;A. Sánchez-Migallón
通过银盐 AgX（X = BF 4、PF 6、CF 3SO 3）和式 AgLX（1-6）的 2,4-二氨基-6-R-1,3,5-三嗪 L（R = 苯基和对甲苯基）的自组装获得了新的配位聚合物。还合成了不同化学计量的配合物[Ag 3L 2(H 2O)(丙酮) 2](BF 4) 3, 7 (R = 苯基)。通过 X 射线衍射研究确定了五种化合物的三维结构。对于AgLX配合物，当X=BF 4 且R=苯基或对甲苯基时，形成Ag和L交替的手性链。这些链通过氢键和弱 Ag...F 相互作用以三维方式与反阴离子交联，从而形成具有溶剂填充通道的结构。当抗衡阴离子为CF 3SO 3 (OTf) 时，发现了不同且更紧凑的结构。当R = 苯基时，形成由具有双三氟甲磺酸酯桥的[Ag 2(OTf) 2L 2]单元组成并且包含π-π堆叠芳烃柱的片层。氢键连接片材。当使用 AgOTf 并且 R 是对甲苯基时，会获得不同且不寻常的梯状结构，其中梯级是双不对称桥，由以 kappa (2) O,mu 2- O 和 kappa (1) O,mu 2- O 方式与 Ag 键合的三氟甲磺酸酯基团组成。这些梯子彼此平行，并通过 N-H...N 氢键相互连接，形成 3D 架构。 7 具有非常相似的梯状结构，但有一个水分子和一个 BF 4 (-) 基团充当桥梁。配合物 6 中氢键形成 3-D 结构的作用在配合物 7 中由 [Ag(丙酮) 2] 片段发挥。非共价相互作用在不同的固态 3D 结构中发挥着重要作用。还分析了新衍生物在溶液中的行为。在低温下检测到了一种新物种，这表明苯环的旋转受到限制。
New coordination polymers have been obtained by the self-assembly of silver salts AgX (X = BF 4, PF 6, CF 3SO 3) and 2,4-diamino-6-R-1,3,5-triazines L (R = phenyl and p-tolyl) of formulas AgLX ( 1- 6). A complex of different stoichiometry, [Ag 3L 2(H 2O)(acetone) 2](BF 4) 3, 7 (R = phenyl), has also been synthesized. The three-dimensional structures of five compounds have been determined by X-ray diffraction studies. For the AgLX complexes, when X = BF 4 and R = phenyl or p-tolyl, chiral chains with alternating Ag and L are formed. The chains are cross-linked by the counteranions in a three-dimensional fashion through hydrogen bonds and weak Ag...F interactions giving rise to a structure with solvent-filled channels. Different and more compact structures have been found when the counteranion is CF 3SO 3 (OTf). When R = phenyl, sheets are formed which consist of [Ag 2(OTf) 2L 2] units with double triflate bridges and which contain columns of pi-pi stacked arenes. Hydrogen bonds connect the sheets. When AgOTf is used and R is p-tolyl, a different and unusual ladderlike structure is obtained in which the rungs are double asymmetric bridges consisting of the triflate groups bonded to Ag in kappa (2) O,mu 2- O and kappa (1) O,mu 2- O fashion. The ladders are parallel to each other and are mutually linked by N-H...N hydrogen bonds to give a 3D architecture. A very similar ladderlike structure has been found for 7 but with a water molecule and a BF 4 (-) group acting as bridges. The role played by the hydrogen bonds in complex 6 to form the 3-D structure is played in 7 by [Ag(acetone) 2] fragments. The noncovalent interactions play an important role in the different solid-state 3D structures. The behavior of the new derivatives in solution has also been analyzed. A new species has been detected at low temperatures, and this exhibits restricted rotation of the phenyl ring.