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The Preparation of Luminescent, Mechanochromic Molecular Containers from Non-Emissive Components: The Box Cations, [Au 6 (Triphos) 4 Br] 5+ and [Au 6 (Triphos) 4 Br 2 ] 4

Daniel T Walters, Xian B Powers, Marilyn M Olmstead, Alan L Balch

Chemistry. 2019 Mar 12;25(15):3849-3857.

PMID: 30575132

Abstract:

Two new molecular boxes, the mono-bromo box [Au6 (Triphos)4 Br](SbF6 )5 ⋅6(CH2 Cl2 ), 4 mB, and the dibromo box, [Au6 (Triphos)4 Br2 ⋅H2 O](SbF6 )4 ⋅4(CH2 Cl2 ), 5 dB, have been prepared in crystalline form. Although constructed from non-luminescent components, both are strongly luminescent. Like its chloro counterpart, the mono-bromo box [Au6 (Triphos)4 Br](SbF6 )5 ⋅6(CH2 Cl2 ), 4 mB, is mechanochromic. Under grinding, it loses its luminescence. The bromo-bridged helicate, [(μ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ), 3μ-H, with a cation that is isomeric with the box [Au6 (Triphos)4 Br]5+ , has also been prepared and crystallographically characterized. Unlike its chloro analogue, [(μ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ) is not luminescent. Thus, the cation produced upon grinding may be the cation present in the bromo-bridged helicate, [(μ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ), 3μ-H. The dibromo box, [Au6 (Triphos)4 Br2 ⋅H2 O](SbF6 )4 ⋅4(CH2 Cl2 ), 5 dB, is not significantly mechanochromic.

Chemicals Related in the Paper:

Catalog Number Product Name Structure CAS Number Price
AP28343615 2,4,5-Trichloro-6-hydroxyisophthalonitrile 2,4,5-Trichloro-6-hydroxyisophthalonitrile 28343-61-5 Price
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