Issue 24, 2015

The effect of gold(i) coordination on the dual fluorescence of 4-(dimethylamino)pyridine

Abstract

The reactions of 4(dimethylamino)pyridine (DMAP) with the gold(I) precursors [AuR(tht)] (R = C6F5, C6Cl2F3 or C6Cl5; tht = tetrahydrothiophene) lead to complexes [AuR(DMAP)] (R = C6F5 (1), C6Cl2F3 (2) or C6Cl5 (3)). X-ray diffraction studies of the complexes reveal the presence of discrete molecules in which aurophilic contacts are absent, with π-stacking (1) or hydrogen bond (2) interactions being responsible for the supramolecular arrangements found in the solid state. All complexes display fluorescence in solution in solvents of different polarities such as toluene, chloroform or acetonitrile. In all cases the emission energy is similar to the low-energy Twisted Intramolecular Charge Transfer (TICT) emission of free DMAP. TDDFT calculations confirm that the fluorescence of complexes 1–3 arises from the ICT excited state of bonded DMAP in which a 90° distortion of the pyridine ring and –NMe2 planes is observed. Model calculations based on experimental parameters show a higher degree of polarization of DMAP upon coordination to Au(I) organometallic fragments.

Graphical abstract: The effect of gold(i) coordination on the dual fluorescence of 4-(dimethylamino)pyridine

Supplementary files

Article information

Article type
Paper
Submitted
09 Feb 2015
Accepted
24 Apr 2015
First published
21 May 2015

Dalton Trans., 2015,44, 11029-11039

The effect of gold(I) coordination on the dual fluorescence of 4-(dimethylamino)pyridine

J. M. López-de-Luzuriaga, E. Manso, M. Monge, M. E. Olmos, M. Rodríguez-Castillo and D. Sampedro, Dalton Trans., 2015, 44, 11029 DOI: 10.1039/C5DT00584A

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