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Inorg Chem. 2011 Feb 21;50(4):1506-12. doi: 10.1021/ic1020719. Epub 2011 Jan 7.

Coordination-driven self-assembly of M3L2 trigonal cages from preorganized metalloligands incorporating octahedral metal centers and fluorescent detection of nitroaromatics.

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  • 1Department of Chemistry, University of Utah, 315 South 1400 East Salt Lake City, Utah 84112, United States.


The design and preparation of novel M(3)L(2) trigonal cages via the coordination-driven self-assembly of preorganized metalloligands containing octahedral aluminum(III), gallium(III), or ruthenium(II) centers is described. When tritopic or dinuclear linear metalloligands and appropriate complementary subunits are employed, M(3)L(2) trigonal-bipyramidal and trigonal-prismatic cages are self-assembled under mild conditions. These three-dimensional cages were characterized with multinuclear NMR spectroscopy ((1)H and (31)P) and high-resolution electrospray ionization mass spectrometry. The structure of one such trigonal-prismatic cage, self-assembled from an arene ruthenium metalloligand, was confirmed via single-crystal X-ray crystallography. The fluorescent nature of these prisms, due to the presence of their electron-rich ethynyl functionalities, prompted photophysical studies, which revealed that electron-deficient nitroaromatics are effective quenchers of the cages' emission. Excited-state charge transfer from the prisms to the nitroaromatic substrates can be used as the basis for the development of selective and discriminatory turn-off fluorescent sensors for nitroaromatics.

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