DESIGN AND FUNCTION OF THE SELF-ASSEMBLED NANO-RINGS

自组装纳米环的设计和功能

• 批准号: 14540543
• 负责人: HABATA Yoichi
• 金额: $ 2.24万
• 依托单位: TOHO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540543/
• 关键词: Silver ion; Amine; Pyridine; Ligand; Suplamolecule; Self-assembly; Macrocyclic; Polymer; ナノリング; 銀

In order to construct the nano-sized polygons or polyhedra by the combination of Ag^+ and flexible aromatic amine ligands, we decided to use N, N'-bis(4-pyridyl)benzylamine (1). B3LYP/3-21G calculations after the conformation analysis by MMFF of 1 showed that the N_<(1)>-N_<(2)>-N_<(3)> angle of the most stable conformer is about 109.7°, which is exactly the same as that of X-ray structure of ligand 1. The Ag^+ induced ^1H-NMR and UV-VIS titration experiments were carried out in order to investigate the stoichiometry between Ag^+ and 1 in solution. Both titration results suggest that ligand 1 forms a (1:1)_n complex with Ag^+ ion in solution. A solid 1-AgOTf complex was obtained by mixing equimolar amount of ligand 1 in CH_3CN and AgOTf in CH_3OH in an N_2 atmosphere. After two days, single crystals precipitated quantitatively. The stoichiometry between ligand 1 and Ag^+ ion in the complex was studied by FAB-MS using m-nitrobenzyl alcohol. The FAB-MS also suggests that the stoichiometr … More y between ligand 1 and Ag^+ in the complex is (1:1)_n. The X-ray crystallography of 1-AgOTf complex was measured at 90K. The complex is a discrete cyclic hexamer (1:Ag^+ = 6:6) including six OTf ions and the hexamer is in the form of a hexagon. There is a large cavity in the center of the complex. Because of the disorder of atoms in the cavity, the solvent atoms in the cavity were not specified at 90K. The diameter of the cavity is about 20Å (Ag-Ag distance: 21.2Å and N_<(2)>-N_<(2')> distance: 21.7Å). Interestingly, the hexagon is not planer, but forms a chair conformation somewhat like the chair-form of cyclohexane. The N_<(2)> atoms are at the corners of the chair structure. The N_<(1)>-N_<(2)>-N_<(3)> and the N_<(1)>-Ag-N_<(3')> bond angles in the complex are 109.7° and 170°, respectively. A nano chair at the center overlaps with six nano chairs from one side, and a total twelve nano chairs from both sides. The nano chairs stack on each other and make honeycomb-like cavities. The atoms that participate overlapped sites are shown by ball-and-stick models. There are two kinds of face-to-face π-π stacking (pyridine-pyridine stacking: yellow-blue, benzene-benzene stacking: yellow-red) sites. The carbon-carbon distances and Ag^+-Ag^+ distances are 3.26-3.67 and 3.41Å, respectively. These carbon-carbon and Ag^+-Ag^+ distances are comparable to those observed in the infinite network systems described previously. In this complex, Ag^+-p interactions were not observed. Stang et al. reported that the angular bidentate ligands having 109.5° angles form pentagon, trigonal bipyramide, adamantanoid or cuboctahedron in self-assembly systems using Pd^<2+> and Pt^<2+> ions, and hexagonal macrocyclic systems need angular bidentate ligands having 120° angles. Less

为了通过Ag^+和柔性芳香胺配体的组合构建纳米尺寸的多边形或多面体，我们决定使用N,N'-双(4-吡啶基)苄胺(1) B3LYP/3-21G计算。经过1的MMFF构象分析表明，最稳定构象异构体的N_<(1)>-N_<(2)>-N_<(3)>角约为109.7°，与配体1的X射线结构完全相同。为了研究Ag^+与1的化学计量关系，进行了Ag^+诱导^1H-NMR和UV-VIS滴定实验。两个滴定结果表明配体 1 与溶液中的 Ag^+ 离子形成 (1:1)_n 络合物，通过混合等摩尔量的配体获得固体 1-AgOTf 络合物。 1 在 CH_3CN 和 AgOTf 在 CH_3OH 中在 N_2 气氛中 两天后，单晶定量沉淀 通过 FAB-MS 使用间硝基苯甲醇研究配体 1 和 Ag^+ 离子之间的化学计量。还表明配合物中配体 1 和 Ag^+ 之间的化学计量 y 为 (1:1)_n。 1-AgOTf 复合物的晶体学在 90K 下测量，该复合物是包含六个 OTf 离子的离散环状六聚体（1:Ag^+ = 6:6），并且六聚体呈六边形形式。由于空腔中原子的无序性，空腔中的溶剂原子在90K时没有指定，空腔的直径约为20Å。 （Ag-Ag 距离：21.2Å 和 N_<(2)>-N_<(2')> 距离：21.7Å）。 (1)>-N_<(2)>-N_<(3)> 和复合物中的N_<(1)>-Ag-N_<(3')>键角分别为109.7°和170°，中心的纳米椅与一侧的6个纳米椅重叠，总共12个纳米椅。纳米椅子相互堆叠并形成蜂窝状空腔，通过球棒模型显示参与重叠位置的原子有两种面对面的π-π堆叠。 （吡啶-吡啶堆积：黄-蓝色，苯-苯堆积：黄-红色）位点的碳-碳距离和Ag^+-Ag^+距离分别为3.26-3.67和3.41Å。 ^+ 距离与之前描述的无限网络系统中观察到的距离相当，在该复合体中，没有观察到 Ag^+-p 相互作用。在使用Pd^<2+>和Pt^<2+>离子的自组装体系中，具有109.5°角的有角二齿配体形成五边形、三方联吡酰胺、金刚烷或立方八面体，而六角大环体系需要具有120°角的有角二齿配体。较少的

项目成果

Y.Habata, S.Yamada: "Molecular structure of the silver(I) triflate complex with N, N', N'', N'''-tetrakis(3',5'-difluorobenzyl)-1,4,8,11-Tetraazacyclotetradecane."J.Include.Phenom, Macrocyclic.Chem.. (in press). (2004)

Y.Habata、S.Yamada：“三氟甲磺酸银 (I) 与 N、N、N、N-四(3,5-二氟苄基)-1,4,8 络合物的分子结构

Yoichi Habata, Sachiko Yamada: "Molecular Structure of the Silver(l)Tri・ate Complex with N,N',N'',N'''-tetrakis(3',5'-difuorobenzyl)-1,4,8,11-tetraazacyclotetradecane"J.Incl.Phenom.and Macrocyclic Chem.. (2004)

Yoichi Habata、Sachiko Yamada：“N,N,N,N-四(3,5-二氟苄基)-1,4,8 银(l)三酸配合物的分子结构,11-四氮杂环十四烷”J.Incl.Phenom.and MacrocycloChem.. (2004)

Yoichi Habata, Yoji Fukuda, Sadatoshi, Akabori, Jerald S.: "Alkali metal ion selectivities of podands that form pseudo-cyclic structures by Intermolecular hydrogen bonding"J.Chem.Soc., Perkin Trans.1. 865-869 (2002)

Yoichi Habata、Yoji Fukuda、Sadatoshi、Akabori、Jerald S.：“通过分子间氢键形成假环状结构的荚果的碱金属离子选择性”J.Chem.Soc.，Perkin Trans.1。

Yoichi Habata, Yoji Fukuda, Sadatoshi Akabori, Jerald S.Bradshaw: "Alkali metal ion selectivities of podands that form pseudo-cyclic structures by Interraolecular hydrogen bonding"J.Chem.Soc., Perkin Trans.1. 865-869 (2002)

Yoichi Habata、Yoji Fukuda、Sadatoshi Akabori、Jerald S.Bradshaw：“通过分子间氢键形成假环状结构的荚体的碱金属离子选择性”J.Chem.Soc.，Perkin Trans.1。

Y.Habata, Y.Fukuda, S.Akabori, J.S.Bradshaw: "Alkali metal ion selectivities of podands that form pseudo-cyclic structures by intermolecular hydrogen bonding."J.Chem.Soc, Perking Trans.. 1. 865-869 (2002)

Y.Habata，Y.Fukuda，S.Akabori，J.S.Bradshaw：“通过分子间氢键形成假环状结构的荚果的碱金属离子选择性。”J.Chem.Soc，Perking Trans.. 1. 865-869（