Water-Soluble and Ultrastable Ti4L6 Tetrahedron with Coordination Assembly Function

We have successfully constructed a tetrahedral Ti4L6 cage with calixarene-like coordination-active vertices. It further features high solubility and stability in H2O and DMF/H2O solution, affording an interesting stepwise assembly function with other metal ions. Through trapping of different amounts...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2017-11, Vol.139 (46), p.16845-16851
Main Authors: He, Yan-Ping, Yuan, Lv-Bing, Chen, Guang-Hui, Lin, Qi-Pu, Wang, Fei, Zhang, Lei, Zhang, Jian
Format: Article
Language:English
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Summary:We have successfully constructed a tetrahedral Ti4L6 cage with calixarene-like coordination-active vertices. It further features high solubility and stability in H2O and DMF/H2O solution, affording an interesting stepwise assembly function with other metal ions. Through trapping of different amounts of Co or Ln ions, the Ti4L6 tetrahedra can be organized into various dimensional architectures, including a Ti4L6-Co3 cage, a Ti4L6-Ln2 cage, a Ti4L6-Ln2 chain, and a three-dimensional Ti4L6-Ln framework. An unusual mixed-valence phenomenon was observed in the Ti4L6 cage, whose Ti3+/4+ compositions were adequately identified by electron spin resonance and X-ray photoelectron spectroscopy analyses. More remarkably, the calixarene-like oxygen vertices of the Ti4L6 cage can also be used for the recognition of C 3-symmetric dye molecules through N–H···O hydrogen bonding. Accordingly, driven by visible light, selective and efficient homogeneous photodecomposition of acid blue 93 and alkali blue 4B were successfully achieved. Therefore, this work not only represents a milestone in constructing symmetric Ti-based cages with interesting coordination assembly function but also provides a new method for preparing technologically important soluble photoactive cages.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b09463