Department of Chemistry, University of Otago, PO Box 56, Dunedin, 9054, New Zealand.
School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland, 1142, New Zealand.
Angew Chem Int Ed Engl. 2020 Jun 26;59(27):11101-11107. doi: 10.1002/anie.202003220. Epub 2020 Apr 30.
A strategy is presented that enables the quantitative assembly of a heterobimetallic [PdPtL ] cage. The presence of two different metal ions (Pd and Pt ) with differing labilities enables the cage to be opened and closed selectively at one end upon treatment with suitable stimuli. Combining an inert Pt tetrapyridylaldehyde complex with a suitably substituted pyridylamine and Pd ions led to the assembly of the cage. H and DOSY NMR spectroscopy and ESI mass spectrometry data were consistent with the quantitative formation of the cage, and the heterobimetallic structure was confirmed using single-crystal X-ray crystallography. The structure of the host-guest adduct with a 2,6-diaminoanthraquinone guest molecule was determined. Addition of N,N'-dimethylaminopyridine (DMAP) resulted in the formation of the open-cage [PtL ] compound and [Pd(DMAP) ] complex. This process could then be reversed, with the reformation of the cage, upon addition of p-toluenesulfonic acid (TsOH).
提出了一种策略，能够实现异双金属 [PdPtL] 笼的定量组装。由于存在两种不同的金属离子（Pd 和 Pt），其稳定性不同，因此可以在合适的刺激下选择性地在一端打开和关闭笼。将惰性 Pt 四吡啶醛配合物与适当取代的吡啶胺和 Pd 离子结合，导致笼的组装。1H 和 DOSY NMR 光谱和 ESI 质谱数据一致表明笼的定量形成，并且使用单晶 X 射线晶体学证实了异双金属结构。确定了与 2,6-二氨基蒽醌客体分子的主体 - 客体加合物的结构。添加 N,N'-二甲氨基吡啶（DMAP）导致形成开笼 [PtL] 化合物和 [Pd（DMAP）] 配合物。然后可以通过添加对甲苯磺酸（TsOH）来逆转该过程，从而重新形成笼。
