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Mixed-Metal Coordination Cages Constructed with Pyridyl-Functionalized β-Diketonate Metalloligands: Syntheses, Structures and Host-Guest Properties

The design and synthesis of mixed‐metal coordination cages, which can act as hosts to encapsule guest molecules, is a subject of intensive research, and the utilization of metalloligand is an effective method to construct a designed heterometallic architecture. Herein, a series of heterometallic cag...

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Bibliographic Details
Published in:Chemistry : a European journal 2015-10, Vol.21 (42), p.14893-14900
Main Authors: Zhang, Ying-Ying, Zhang, Long, Lin, Yue-Jian, Jin, Guo-Xin
Format: Article
Language:English
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Summary:The design and synthesis of mixed‐metal coordination cages, which can act as hosts to encapsule guest molecules, is a subject of intensive research, and the utilization of metalloligand is an effective method to construct a designed heterometallic architecture. Herein, a series of heterometallic cages with half‐sandwich Rh, Ir and Ru fragments using CuII‐metalloligand as a building block by a stepwise approach is reported. The cavity sizes of the cages could be controlled easily by the lengths of the organic ligands. Because the metalloligands in the oxalate‐based cage are somewhat distorted and concave, there are weak Cu⋅⋅⋅O interactions in the molecules, forming a binuclear copper unit. By increasing the height of the cages using longer ligands, 2,5‐dichloro‐3,6‐dihydroxy‐1,4‐benzoquinone (H2CA), the organometallic boxes display interesting host–guest behavior, which are made large enough to accommodate some large molecules, such as pyrene and [Pt(acac)2]. Interestingly, the heterometallic cage with larger cavity size can transfer into a homometallic hexanuclear prism in the presence of pyrazine. Rattling the cage: A series of cages with half‐sandwich Rh, Ir and Ru fragments were prepared using CuII‐metalloligand components by a stepwise approach. The cavity size could be controlled easily by the length of the organic ligands. The cages with larger cavity sizes were found to accommodate some large guest molecules.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201502194