Anion-, Solvent-, Temperature-, and Mechano-Responsive Photoluminescence in Gold(I) Diphosphine-Based Dimers

Deák, Andrea Beáta and Jobbágy, Csaba and Marsi, Gábor and Molnár, Miklós and Szakács, Zoltán and Baranyai, Péter (2015) Anion-, Solvent-, Temperature-, and Mechano-Responsive Photoluminescence in Gold(I) Diphosphine-Based Dimers. CHEMISTRY-A EUROPEAN JOURNAL, 21 (32). pp. 11495-11508. ISSN 0947-6539

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Abstract

We synthesized and characterized a series of [Au 2 (nixantphos) 2 ](X) 2 (nixantphos = 4,6 - bis(diphenylphosphino) - phenoxazine; X = NO 3 , 1 ; CF 3 COO, 2 ; CF 3 SO 3 , 3 ; [Au(CN) 2 ], 4 ; and BF 4 , 5 ) complexes, which exhibit intriguing anion - switchable and stimuli - responsive luminescent photophysical properties. Depending on their anions these complexes display yellow ( 3 ), orange ( 4 and 5 ) and red ( 1 and 2 ) emission colours. They exhibit reversible thermochromic, mechanochrom ic and vapochromic luminescence changes readily perceivable by the naked eye. Single crystal X - ray studies show that the [Au 2 (nixantphos) 2 ] 2+ cations with short intramolecular Au···Au interactions are involved as donors in infinite N−H···X (X = O and N) hydrogen bonded chain formation with CF 3 COO – ( 2C ) and aurophilically linked [Au(CN) 2 ] – counter ions ( 4C ). Both crystals show thermochromic luminescence, as their room temperature red ( 2C ) and orange ( 4C ) emission turns into y ellow upon cooling to 77 K. They also exhibit reversible mechanochromic luminescence by changing their emission colour from red to dark ( 2C ), and orange to red ( 4C ). Compounds 1 – 5 also display reversible mechanochromic luminescence altering their emission colours between orange ( 1 ) or red ( 2 ) to dark, as well as between yellow ( 3 ) or orange ( 4 and 5 ) to red. Detailed photophysical investigations and correlation with solid - state structural data established the significant role of N−H···X interactions in the stimuli - responsive luminescent behaviour.

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