Journal
NATURE COMMUNICATIONS
Volume 11, Issue 1, Pages -Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/s41467-019-13682-5
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Funding
- National Natural Science Foundation of China [21822107, 91961105, 21571115, 21827801]
- Natural Science Foundation of Shandong Province [JQ201803, ZR2019ZD45, ZR2017MB061]
- Taishan Scholar Project of Shandong Province of China [tsqn201812003, ts20190908]
- Qilu Youth Scholar Funding of Shandong University
- Fundamental Research Funds of Shandong University [104.205.2.5]
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Thiacalix[4]arenes as a family of promising ligands have been widely used to construct polynuclear metal clusters, but scarcely employed in silver nanoclusters. Herein, an anion-templated Ag-88 nanocluster (SD/Ag88a) built from p-tert-butylthiacalix[4]arene (H(4)TC4A) is reported. Single-crystal X-ray diffraction reveals that C-4-symmetric SD/Ag88a resembles a metal-organic super calix comprised of eight TC4A(4-) as walls and 88 silver atoms as base, which can be deconstructed to eight [CrO4@Ag-11(TC4A)(EtS)(4)(OAc)] secondary building units arranged in an annulus encircling a CrO42- in the center. Local and global anion template effects from chromates are individually manifested in SD/Ag88a. The solution stability and hierarchical assembly mechanism of SD/Ag88a are studied by using electrospray mass spectrometry. The Ag-88 nanocluster represents the highest nuclearity metal cluster capped by TC4A(4-). This work not only exemplify the specific macrocyclic effects of TC4A(4-) in the construction of silver nanocluster but also realize the shape heredity of TC4A(4-) to overall silver super calix.
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