Homochiral column structure of rac- and Λ-[MIII(tn) 3]P3O9 (M = Co, Cr; Tn = 1,3-diaminopropane; P3O9 = cyclotriphosphate(3-)) produced by multiple hydrogen bonds
Homochiral column structure of rac- and Λ-[MIII(tn) 3]P3O9 (M = Co, Cr; Tn = 1,3-diaminopropane; P3O9 = cyclotriphosphate(3-)) produced by multiple hydrogen bonds
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由多个氢键产生的 rac- 和 Λ-[MIII(tn) 3]P3O9（M = Co, Cr；Tn = 1,3-二氨基丙烷；P3O9 = 环三磷酸（3-））的同手性柱结构
DOI：
10.1039/c0nj00270d
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发表时间：
2010
影响因子：
3.3
通讯作者：
F. Galsbøl
中科院分区：
文献类型：
--
作者：
Y. Sunatsuki;S. Miyahara;Takayoshi Suzuki;M. Kojima;T. Nakashima;N. Matsumoto;F. Galsbøl
用单晶X射线衍射法测定了外消旋-和Λ-[MIII（tn）3] P3 O 9·nH 2 O（M = Co，Cr; tn = 1，3-丙二胺=三亚甲基二胺; P3 O 9 =环三磷酸（3-））的晶体结构。在rac-[Co（tn）3] P3 O 9·7. 3 H2O中，具有相同绝对构型（Δ或Λ）的[Co（tn）3]3+阳离子和P3 O 93-阴离子交替排列，并通过多个NH + O氢键连接，形成纯手性柱状结构。具有相反手性的相邻纯手性柱通过柱间氢键连接以形成外消旋柱对。外消旋-[Cr（tn）3] P3 O 9·7.5H2O的晶体结构与Co配合物相似，但存在两种外消旋柱对。在Λ-[Co（tn）3] P3 O 9·2.5H2O晶体中，一对由交替堆叠的Λ-[Co（tn）3]3+阳离子和P3 O 93-阴离子组成的柱通过氢键连接。相邻的柱对通过氢键进一步连接以形成三维（3-D）片结构。Λ-[Cr（tn）3] P_3O_9·2.5H_2O的晶体结构与Co配合物是类质同象的。加入P3 O 93-后，Λ-[M（tn）3] Br 3（M = Co、Cr）水溶液的圆二色性（CD）光谱发生变化，并通过氢键形成离子对来解释这种变化。
The crystal structures of rac- and Λ-[MIII(tn)3]P3O9·nH2O (M = Co, Cr; tn = 1,3-diaminopropane = trimethylenediamine; P3O9 = cyclotriphosphate(3−)) were determined by single-crystal X-ray analyses. In rac-[Co(tn)3]P3O9·7.3H2O, the [Co(tn)3]3+ cations with the same absolute configuration (Δ or Λ) and the P3O93− anions are alternately arrayed and connected by multiple NH⋯O hydrogen bonds to form a homochiral columnar structure. Adjacent homochiral columns with opposite chirality are connected by intercolumn hydrogen bonds to form a racemic pair of columns. The crystal structure of rac-[Cr(tn)3]P3O9·7.5H2O is similar to that of the Co complex; however, there exist two types of racemic pairs of columns. In the crystal of Λ-[Co(tn)3]P3O9·2.5H2O, a pair of columns consisting of alternately stacked Λ-[Co(tn)3]3+ cations and P3O93− anions are linked by hydrogen bonds. Neighboring column pairs are further linked by hydrogen bonds to form a three-dimensional (3-D) sheet structure. The crystal structure of Λ-[Cr(tn)3]P3O9·2.5H2O is isomorphous with the Co complex. The circular dichroism (CD) spectra of aqueous solutions of Λ-[M(tn)3]Br3 (M = Co, Cr) change when P3O93− is added, and the changes were explained by ion pair formation through hydrogen bonds.
影响因子：
4.6
作者：
Hirofumi Nakamura;Y. Sunatsuki;M. Kojima;N. Matsumoto
通讯作者：
Hirofumi Nakamura;Y. Sunatsuki;M. Kojima;N. Matsumoto