Reger Daniel L, Semeniuc Radu F, Rassolov Vitaly, Smith Mark D
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA.
Inorg Chem. 2004 Jan 26;43(2):537-54. doi: 10.1021/ic035207i.
The bitopic ligand p-C(6)H(4)CH(2)OCH(2)C(pz)(3) (pz = pyrazolyl ring) that contains two tris(pyrazolyl)methane units connected by a semirigid organic spacer reacts with silver(I) salts to yield p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgX)(2), where X = CF(3)SO(3)(-) (1), SbF(6)(-) (2), PF(6)(-) (3), BF(4)(-) (4), and NO(3)(-) (5). Crystallization of the first three compounds from acetone yields p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgCF(3)SO(3))(2) (1a), p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgSbF(6))(2)(CH(3))(2)CO (2b), and p-C(6)H(4)CH(2)OCH(2)C(pz)(3)AgPF(6) (3a), where the stoichiometry for the latter compound has changed from a metal:ligand ratio of 2:1 to 1:1. The structure of 1a is based on helical argentachains constructed by a kappa(2)-kappa(1) coordination to silver of the tris(pyrazolyl)methane units. These chains are organized into a tubular 3D structure by cylindrical (CF(3)SO(3))(6)(-) clusters that form weak C-H...O hydrogen bonds with the bitopic ligand. The same kappa(2)-kappa(1) coordination is present in the structure of 2a, but the structure is organized by six different tris(pyrazolyl)methane units from six ligands bonding with six silvers to form a 36-member argentamacrocycle core. The cores are organized in a tubular array by the organic spacers where each pair of macrocycles sandwich six acetone molecules and one SbF(6)(-) counterion. The structure of 3a is based on a kappa(2)-kappa(0) coordination mode of each tris(pyrazolyl)methane unit forming a helical coordination polymer, with two strands organized in a double stranded helical structure by a series of C-H...pi interactions between the central arene rings. Crystallization of 2-4 from acetonitrile yields complexes of the formula p-C(6)H(4)CH(2)OCH(2)C(pz)(3)[(AgX)(2)(CH(3)CN)(n)] where n = 2 for X = SbF(6)(-) (2b), X = PF(6)(-) (3b) and n = 1 for X = BF(4)(-) (4b). All three structures contain argentachains formed by a kappa(2)-kappa(1) coordination mode of the tris(pyrazolyl)methane units linked by the organic spacer and arranged in a 2D sheet structure with the anions sandwiched between the sheets. Crystallization of 5 from acetonitrile yields crystals of the formula p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgNO(3))(2)(CH(3)CN)(4), where the nitrate is bonded to the silver. The argentachains, again formed by kappa(2)-kappa(1) coordination, are arranged in W-shaped sheets that have an overall configuration very different from 2b-4b. Treating p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgSbF(6))(2) with a saturated aqueous solution of KPF(6) or KO(3)SCF(3) slowly leads to complete exchange of the anion. Crystallization of a sample that contains an approximately equal mixture of SbF(6)(-)/PF(6)(-) from acetonitrile yields p-C(6)H(4)CH(2)OCH(2)C(pz)(3)[Ag(2)(PF(6))(0.78(1))(SbF(6))(1.22(1))(CH(3)CN)(2)][(CH(3)CN)(0.25) (C(4)H(10)O)(0.25)], a compound with a sheet structure analogous to 2b-4b. Crystallization of the same mixture from acetone yields p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgSbF(6))(CH(3))(2)CO, where the metal-to-ligand ratio is 1:1 and the [C(pz)(3)] units are kappa(2)-kappa(0) bonded forming a coordination polymer. The supramolecular structures of all species are organized by a combination of C-H...pi, pi-pi, or weak C-H-F(O) hydrogen bonding interactions.
双位点配体对苯撑 - C(6)H(4)CH(2)OCH(2)C(pz)(3)（pz = 吡唑基环）含有两个通过半刚性有机间隔基相连的三（吡唑基）甲烷单元，它与银（I）盐反应生成 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgX)(2)，其中 X = CF(3)SO(3)(-)（1）、SbF(6)(-)（2）、PF(6)(-)（3）、BF(4)(-)（4）和 NO(3)(-)（5）。前三种化合物从丙酮中结晶得到 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgCF(3)SO(3))(2)（1a）、p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgSbF(6))(2)(CH(3))(2)CO（2b）和 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)AgPF(6)（3a），其中后一种化合物的化学计量比从金属与配体的 2:1 变为 1:1。1a 的结构基于由三（吡唑基）甲烷单元以 κ(2)-κ(1) 配位方式与银形成的螺旋状银链。这些链通过圆柱形的 (CF(3)SO(3))(6)(-) 簇组织成管状三维结构，这些簇与双位点配体形成弱的 C-H...O 氢键。2a 的结构中存在相同的 κ(2)-κ(1) 配位，但结构由来自六个配体的六个不同的三（吡唑基）甲烷单元与六个银键合形成 36 元银大环核心。这些核心由有机间隔基排列成管状阵列，其中每对大环夹着六个丙酮分子和一个 SbF(6)(-) 抗衡离子。3a 的结构基于每个三（吡唑基）甲烷单元的 κ(2)-κ(0) 配位模式形成螺旋状配位聚合物，两条链通过中心芳烃环之间的一系列 C-H...π 相互作用组织成双链螺旋结构。2 - 4 从乙腈中结晶得到通式为 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)[(AgX)(2)(CH(3)CN)(n)] 的配合物，其中对于 X = SbF(6)(-)（2b）、X = PF(6)(-)（3b），n = 2，对于 X = BF(4)(-)（4b），n = 1。所有三种结构都包含由三（吡唑基）甲烷单元以 κ(2)-κ(1) 配位模式形成的银链，这些银链通过有机间隔基连接并排列成二维片状结构，阴离子夹在片层之间。5 从乙腈中结晶得到通式为 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgNO(3))(2)(CH(3)CN)(4) 的晶体，其中硝酸盐与银键合。同样由 κ(2)-κ(1) 配位形成的银链排列成 W 形片层，其整体构型与 2b - 4b 非常不同。用 KPF(6) 或 KO(3)SCF(3) 的饱和水溶液处理 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgSbF(6))(2) 会缓慢导致阴离子的完全交换。从乙腈中结晶出含有近似等量 SbF(6)(-)/PF(6)(-) 混合物的样品，得到 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)[Ag(2)(PF(6))(0.78(1))(SbF(6))(1.22(1))(CH(3)CN)(2)][(CH(3)CN)(0.25)(C(4)H(10)O)(0.25)]，一种具有与 2b - 4b 类似片状结构的化合物。从丙酮中结晶出相同混合物得到 p-C(6)H(4)CH(2)OCH(2)C(pz)(3)(AgSbF(6))(CH(3))(2)CO，其中金属与配体的比例为 1:1，且 [C(pz)(3)] 单元以 κ(2)-κ(0) 键合形成配位聚合物。所有物种的超分子结构通过 C-H...π、π-π 或弱的 C-H-F(O) 氢键相互作用的组合来组织。
