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Chemistry. 2012 Jul 2;18(27):8358-65. doi: 10.1002/chem.201200155. Epub 2012 May 25.

Isostructural M2L4 molecular capsules with anthracene shells: synthesis, crystal structures, and fluorescent properties.

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Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Yokohama 226-8503, Japan.


An isostructural series of M(2)L(4) molecular capsules quantitatively self-assembled from two M(II) ions (M=Zn, Cu, Pt, Pd, Ni, Co, and Mn) and four bent ligands with embedded anthracene fluorophores. X-ray crystallographic analysis (for M=Zn, Cu, Ni, and Pd) confirmed the formation of closed-shell structures in which the large interior cavities inside the molecular capsules (about 1 nm) were shielded by eight anthracene panels. Analysis of the Zn(II) and Cu(II) structures showed the inclusion of an unusual triad guest cluster; four MeCN molecules, one water molecule, and one CF(3)SO(3)(-) ion were located inside the cavities. Full characterization by NMR spectroscopy and MS (ESI-TOF) demonstrated that the molecular capsules were quite stable and persist in solution. The fluorescence properties of the isostructural capsules were strongly dependent on the identity of the metal species: the Zn(II) capsule emitted strong blue fluorescence with a high quantum yield (Φ=0.8), in sharp contrast to the weakly emissive Ni(II) and Mn(II) capsules and the completely non-emissive Pd(II), Pt(II), and Co(II) capsules. On the other hand, the Cu(II) capsule exhibited solvatochromism and solvent-dependent emission behavior; blue emission of the capsule was "on" in DMSO but "off" in MeCN.

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