School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT (UK).
Chemistry. 2014 Apr 1;20(14):4117-25. doi: 10.1002/chem.201304437. Epub 2014 Mar 3.
The C3-symmetric chiral propylated host-type ligands (±)-tris(isonicotinoyl)-tris(propyl)-cyclotricatechylene (L1) and (±)-tris(4-pyridyl-4-benzoxy)-tris(propyl)-cyclotricatechylene (L2) self-assemble with Pd(II) into Pd6L8 metallo-cages that resemble a stella octangula. The self-assembly of the Pd6(L1)8 cage is solvent-dependent; broad NMR resonances and a disordered crystal structure indicate no chiral self-sorting of the ligand enantiomers in DMSO solution, but sharp NMR resonances occur in MeCN or MeNO2. The Pd6(L1)8 cage is observed to be less favourable in the presence of additional ligand, than is its counterpart, where L=(±)-tris(isonicotinoyl)cyclotriguaiacylene (L1 a). The stoichiometry of reactant mixtures and chemical triggers can be used to control formation of mixtures of homoleptic or heteroleptic Pd6L8 metallo-cages where L=L1 and L1 a.
具有 C3 对称手性丙基取代主体型配体（±）-三（异烟酰基）-三（丙基）-环三[2.2.2]辛烷（L1）和（±）-三（4-吡啶基-4-苯氧基）-三（丙基）-环三[2.2.2]辛烷（L2）与 Pd(II) 自组装形成类似于八面体星的Pd6L8金属笼。Pd6(L1)8笼的自组装取决于溶剂；宽 NMR 共振和无序晶体结构表明在 DMSO 溶液中配体对映异构体没有手性自分拣，但在 MeCN 或 MeNO2 中出现尖锐的 NMR 共振。与（±）-三（异烟酰基）环三[2.2.2]辛烷（L1a）相比，Pd6(L1)8笼在存在额外配体时不太有利。反应物混合物的化学计量和化学触发可以用于控制同多金属笼或杂多金属笼Pd6L8的混合物的形成，其中 L=L1 和 L1a。
Zotero 插件