| 紫外-可见光谱法研究β-环糊精对短链脂肪胺及其Cu(Ⅱ)、Ni(Ⅱ)配合物的包合行为 |
| Inclusion Behaviors of β-cyclodextrin to Short Chain Aliphatic Amines and Their Coordination Complexes of Cu(Ⅱ) and Ni(Ⅱ) by UV-Vis Spectroscopy |
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| 摘要: 本文首次报道了β-环糊精(β-CD)与一组有机客体及其配合物的包合行为。以β-CD及其衍生物：单[2-氧-(2-甲基)]-β-CD(Mβ-CD)和单[2-氧-(2-羟丙基)]-β-CD(HPβ-CD)为主体，以乙二胺(en，1)、二乙烯三胺(dien，2)、三乙胺(3)、乙二胺四乙酸(4)以及(1)与(2)的配合物[Cu(en)2]Cl2·H2O (5)、[Cu(dien)2]Cl2·H2O (6)、[Ni(en)3]Cl2·1.5H2O (7)和[Ni(dien)2]Cl2·H2O (8)为客体，通过竞争包结法考察了水溶液中β-CD与客体1～4之间的相互作用，4个包合物生成常数的大小具有如下排序：3>2>4>1，客体分子结构上的微小差异譬如不同的链长与侧链是导致它们在水溶液中与β-CD相互作用产生差异的根本原因。此外，本文研究了β-CD，Mβ-CD和HPβ-CD与4个经典配合物5～8形成第二配位层(超分子)包合物的化学计量和生成常数。结果表明，处于第一配位层(配合物)中的中心体和配体的本性，明显影响第二配位层(包合物)中主体与作为客体的配合物之间的包合作用强度。并且主体不同，影响的幅度也不同。 |
| 关键词: 环糊精 乙二胺 超分子 包合物 生成常数 |
| 基金项目: |
| Abstract: The inclusion behaviors of a serial of organic guests and their coordination complexes with β-cyclodextrin (β-CD) were reported. β-CD and its two derivatives, mono(2-O-2-methyl)-β-CD(Mβ-CD) and mono(2-O-2-hydroxypropyl)-β-CD (HPβ-CD), were chosen as hosts, and several organic amines: ethylenediamine 1, diethylenetriamine 2, triethylamine 3 and ethylene diaminetetraacetic acid 4, and the coordination compounds of ligands 1 and 2: [Cu(en)2]Cl2·H2O (5), [Cu(dien)2]Cl2·H2O (6), [Ni(en)3]Cl2·1.5H2O (7) and [Ni(dien)2]Cl2·H2O (8) were chosen as guests. The intermolecular interactions between hosts and guests in aqueous solution were investigated. The formation constants of β-CD inclusion complexes of guests 1～4 decreased in the order: 3 > 3 > 4 > 1, revealing that minor differences in the molecular structure of guests could be effectively recognized by the cavity of β-CD in aqueous solution. The chemical stoichiometries and K values of the supramolecular complexes of guests 5～8 with β-CD, Mβ-CD and HPβ-CD were also determined. The inclusion behaviors of the guests and hosts in the second-sphere complexes were obviously influenced by the fundamental properties of central ions and ligands in the first-sphere coordination compounds. Additionally, the effect varies with hosts. |
| Keywords: cyclodextrin ethylenediamine supermolecule inclusion complex formation constant |
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| 王海名,宋乐新,滕传峰,柏 雷.紫外-可见光谱法研究β-环糊精对短链脂肪胺及其Cu(Ⅱ)、Ni(Ⅱ)配合物的包合行为[J].无机化学学报,2008,24(1):1-9. |
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