金属卡宾模板导向的多咪唑鎓盐大环合成  

Controllable synthesis of polyimidazolium macrocycles based on metal-N-heterocyclic carbene templates

作　　者：王以寿 白莎 王尧宇[1] 韩英锋 WANG Yishou;BAI Sha;WANG Yaoyu;HAN Yingfeng(College of Chemistry and Materials Science,Northwest University,Xi′an 710127,China;School of Chemical Engineering and Modern Materials,Shangluo University,Shangluo,Shaanxi 726000,China)

机构地区：[1]西北大学化学与材料科学学院,西安710127 [2]商洛学院化学工程与现代材料学院,商洛726000

出　　处：《无机化学学报》2024年第1期221-231,共11页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22025107,22301240);陕西省自然科学基础研究计划(No.S2023‐JC‐QN‐1639,2022JQ‐093);陕西基础科学(化学、生物学)研究院科学研究计划项目(No.22JHZ003,22JHQ008)资助。

摘　　要：本文报道了一种共价有机大环化合物的高效合成方法。利用双咪唑鎓盐H_(2)‐L1(BF_(4))_(2)(L1=A1,B1)和氧化银反应,生成双核银卡宾大环化合物[Ag_(2)(L1)_(2)](BF_(4))_(2)(L1=A1,B1),其中连接在2个卡宾配体上的端烯取代基分别排列在环的两侧。随后,通过金属卡宾模板导向的烯烃复分解反应进行关环,制备得到闭环的双核银卡宾大环化合物[Ag_(2)(L2)](BF_(4))_(2)(L2=A2,B2)。最后,移除模板银离子即可得到拥有空腔结构的共价有机大环化合物H_(4)-L2(BF_(4))_(4)(L2=A2,B2)。此类多咪唑鎓盐大环的尺寸和形状可以通过改变氮杂环卡宾前驱体连接单元的长度或者宽度进行精细调节。初步研究表明,该大环受体在碘离子的传感、检测和识别方面具有潜在的应用前景。In this investigation,we have devised a highly proficient methodology for synthesizing covalent organic macrocycles.The reaction involving bisimidazolium salts H_(2)-L1(BF_(4))_(2)(L1=A1,B1) with silver oxide resulted in the formation of binuclear silver metallacycles of the [Ag_(2)(L1)_(2)](BF_(4)_)2(L1=A1,B1) classification.These metallacycles manifest olefinic appendages originating from two discrete dicarbene-bridged ligands arranged in pairs.Successive metal-carbene-templated ring-closing metathesis(RCM) precipitated the generation of two carbon-carbon double bonds connecting the two di-NHC ligands,thereby yielding cyclized binuclear silver metallacycles [Ag_(2)(L2)](BF_(4))_(2)(L2=A2,B2).Subsequent removal of the metal ions led to the formation of covalent organic macrocycles H_(4)-L2(BF_(4))_(4)(L2=A2,B2) with a substantial internal cavity.The dimensions and configuration of these polyimidazolium macrocycles can be facilely manipulated by adjusting the length and breadth of the bridging units in the ligands.Preliminary investigations indicate the potential applicability of this receptor in iodide sensing,detection,and recognition.

关 键 词：模版导向合成 大环化合物 氮杂环卡宾 烯烃复分解反应 

分 类 号：O614.122[理学—无机化学] O626.23[理学—化学]