Alkaline Earth Guests in Polyoxopalladate Chemistry: From Nanocube to Nanostar via an Open-Shell Structure

作者：Yang, Peng; Xiang, Yixian; Lin, Zhengguo; Bassil, Bassem S.; Cao, Jie; Fan, Linyuan; Fan, Yanxuan; Li, Ming-Xing; Jimenez-Lozano, Pablo; Carbo, Jorge J.; Poblet, Josep M.; Kortz, Ulrich^*

来源：Angewandte Chemie - International Edition, 2014, 53(44): 11974-11978.

DOI：10.1002/anie.201407090

• cluster compounds
• palladium
• polyoxometalates
• template effect
• X-ray diffraction

The three novel, discrete palladium(II)-oxo clusters [CaPd12O8(PhAsO3)(8)](6) (CaPd12), [SrPd12O6(OH)(3-) (PhAsO3)(6)(OAc)(3)](4-) (SrPd12), and [BaPd15O10(PhAsO3)(10)](8-) (BaPd15) encapsulating alkaline earth metal ions were prepared and fully characterized by a multitude of solution and solid-state physicochemical techniques. We have discovered a structure-directing template effect induced by the respective size of the alkaline earth guest ion, which determines the detailed condensation arrangement of the peripheral Pd-II-oxo shell. The unprecedented SrPd12 with an open-shell type structure is of particular importance and reflects a successful strategy for deliberate design of new structural classes of polyoxo-noble-metalates. Furthermore, the unusual acetate-water ligand exchange phenomenon renders SrPd12 as a promising candidate for noble-metal-based catalysis.

• 出版日期2014-10-27
• 单位北京理工大学; 上海大学