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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+
Author(s) -
Walters Daniel T.,
Powers Xian B.,
Olmstead Marilyn M.,
Balch Alan L.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805247
Subject(s) - triphos , materials science , luminescence , optoelectronics , metallurgy , metal
Two new molecular boxes, the mono‐bromo box [Au 6 (Triphos) 4 Br](SbF 6 ) 5 ⋅6(CH 2 Cl 2 ), 4 mB , and the dibromo box, [Au 6 (Triphos) 4 Br 2 ⋅H 2 O](SbF 6 ) 4 ⋅4(CH 2 Cl 2 ), 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 [Au 6 (Triphos) 4 Br](SbF 6 ) 5 ⋅6(CH 2 Cl 2 ), 4 mB , is mechanochromic. Under grinding, it loses its luminescence. The bromo‐bridged helicate, [(μ‐Br){Au 3 (Triphos) 2 } 2 ](CF 3 SO 3 ) 5 ⋅2(CH 2 Cl 2 ), 3μ‐H , with a cation that is isomeric with the box [Au 6 (Triphos) 4 Br] 5+ , has also been prepared and crystallographically characterized. Unlike its chloro analogue, [(μ‐Br){Au 3 (Triphos) 2 } 2 ](CF 3 SO 3 ) 5 ⋅2(CH 2 Cl 2 ) is not luminescent. Thus, the cation produced upon grinding may be the cation present in the bromo‐bridged helicate, [(μ‐Br){Au 3 (Triphos) 2 } 2 ](CF 3 SO 3 ) 5 ⋅2(CH 2 Cl 2 ), 3μ‐H . The dibromo box, [Au 6 (Triphos) 4 Br 2 ⋅H 2 O](SbF 6 ) 4 ⋅4(CH 2 Cl 2 ), 5 dB , is not significantly mechanochromic.