Steric Control over Interligand Dihedrals and Splay Leads to the Formation of Fe^(II)_(6)L_(6)and Fe^(II)_(8)L_(8)Antiprisms  

作　　者：Yuchong Yang Yuyin Du Tanya K.Ronson Jonathan R.Nitschke 

机构地区：[1]Yusuf Hamied Department of Chemistry,University of Cambridge,Cambridge CB21EW

出　　处：《CCS Chemistry》2024年第10期2411-2419,共9页中国化学会会刊（英文）

基　　金：supported by the European Research Council(grant no.695009);the UK Engineering and Physical Sciences Research Council(EPSRC,grant nos.EP/T031603/1 and EP/P027067/1).

摘　　要：Macrocycles have found uses in guest capture,sensing,and porous materials,motivating the development of new methods for their synthesis.Here we report the construction of two types of barrelshaped macrocyclic assemblies,with trigonal antiprismatic Fe^(II)_(6)L_(6)and square antiprismatic Fe^(II)_(8)L_(8)architectures,from FeII and boron-containing tritopic ligands.Two factors,the steric hindrance of ligands and the preferred coordination angles at different vertices,were observed to regulate the dihedral angles between adjacent ligands,leading to the formation of the structures observed.The effects of ligand steric hindrance led to the formation of a Fe^(II)_(6)L_(6)trigonal antiprism,which efficiently encapsulated persistent environmental pollutant perfluorosulfonate anions.In contrast with the iminopyridine chelating groups of the Fe^(II)_(6)L_(6)structure,the incorporation of azopyridine moieties coordinated with the FeII centers not only increased the vertex opening angle,resulting in the construction of a Fe^(II)_(8)L_(8)square antiprism,but also enabled the redox-driven reversible disassembly of this structure.The design strategies that have enabled the construction of these antiprismatic macrocycles may provide insight into the design principles governing the formation of more complex functional assemblies.

关 键 词：self-assembly metal-organic cages host-guest chemistry redox-responsive materials dihedral control 

分 类 号：O62[理学—有机化学]