NDLI: Luminescence, structural, and bonding trends upon varying the halogen in isostructural aurophilic dimers

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Luminescence, structural, and bonding trends upon varying the halogen in isostructural aurophilic dimers

Content Provider	Royal Society of Chemistry (RSC)
Author	Bruce, Mitchell R. M. Gonser, M. W. Alexander Elbjeirami, Oussama Bruce, Alice E. Cundari, Thomas R. Stewart, Barbara N. Omary, Mohammad A.
Copyright Year	2009
Abstract	The preparation of three isonitrile complexes (p-tosyl)CH2NCAuIX (X = Cl, Br, and I) along with their structural, spectral, and computational characterization are reported. X-Ray crystallography reveals that these complexes all crystallize in the same space group, C2/c, and have closely related supramolecular structures. The three complexes exhibit crossed-dimer structures with short Au⋯Au aurophilic distances of 3.0634(4) Å, 3.1044(7) Å, and 3.1083(5) Å, for X = Cl, Br, and I, respectively. These distances are among the shortest ligand-unassisted Au⋯Au interactions reported. While RNCAuX complexes that we reported earlier associate as anti-parallel, one-dimensional aurophilic polymers with long Au⋯Au distances (∼3.6 Å) and exhibit orange–red phosphorescence, the analogous aurophilic dimers herein show seemingly counter-intuitive blue–green emissions despite having much shorter Au⋯Au distances. DFT computations are used to augment experiment and study the T1 phosphorescent excited state of [RNCAuX]n in parallel, anti-parallel, and staggered conformations. Excimeric bonding and large Stokes shifts are predicted for all models, the extent of which is sensitive to both “n” and conformation with trends commensurate with experimental luminescence data. Calculations for the three [MeNCAuX]2 dimeric complexes reveal blue–green phosphorescence with a red shift as a function of increasing halide softness, consistent with experimental data for (p-tosyl)CH2NCAuIX (Cl > Br > I). The overall experimental and theoretical work signifies the central role of ground-state aurophilic bonding and excited-state excimeric bonding on the electronic structure, hence facilitating development of structure–luminescence relations that may assist in the rational design of novel optoelectronic devices.
Starting Page	1522
Ending Page	1533
Page Count	12
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	0
Issue Number	9
Journal	Dalton Transactions
DOI	10.1039/b813875c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Stokes Isocyanide X-ray crystallography Space group Phosphorescence Conformational isomerism Luminescence Halogen Optoelectronics
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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