Metal-metal stacking patterns between and with [Pt(tpy)X]+ cations
- Phillips, V. 1
- Baddour, F.G. 1
- Lasanta, T. 2
- López-De-Luzuriaga, J.M. 2
- Bacon, J.W. 1
- Golen, J.A. 34
- Rheingold, A.L. 3
- Doerrer, L.H. 1
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1
Boston University
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2
Universidad de La Rioja
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3
University of California, San Diego
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4
University of Massachusetts Dartmouth
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ISSN: 0020-1693
Año de publicación: 2010
Volumen: 364
Número: 1
Páginas: 195-204
Tipo: Artículo
Otras publicaciones en: Inorganica Chimica Acta
Resumen
A comparative study of metallophilic interactions of [Pt(tpy)X]+ cations (tpy = 2,2′:6′,2″-terpyridine) in the presence of two different types of anions, (i) [AuX2′]- anions that form double salts and (ii) simple p-block anions, is reported. Single-crystal X-ray diffraction data, solution-state 195Pt NMR spectra, and variable temperature solid-state luminescence spectra are reported. Three [Pt(tpy)Cl]Y derivatives (Y = SbF6, 1, SbF6·CH3CN, 4, PF6, 2) and the [Pt(tpy)Br]PF6 analog, 3, as well as two new double salts [Pt(tpy)CN][Au(CN)2], 5, and [Pt(tpy)CN] 2[Au(C6F5)2](PF6), 6, have been synthesized and characterized. Structural analysis shows consistent patterns in Pt···Pt interactions that vary slightly depending on the coordinating halogen or pseudo-halogen X, counter anion Y, and lattice solvent. Metallophilic interactions are seen between [Pt(tpy)X] + cations with all types of X ligands, but only with π-accepting X′ ligands from [AuX2′]- anions are Pt⋯Au metallophilic interactions seen to be favored over Pt⋯Pt interactions. The [Au(CN)2]- anion consistently forms Pt···Au metallophilic contacts, unlike [Au(C 6F5)2]-. The 195Pt NMR chemical shifts are ∼-2750 ppm for π-donor ligands and near -3120 ppm for π-acceptor ligands in [Pt(tpy)X]PF6 compounds. Luminescence data show an unusual blue shift in [Pt(tpy)CCPh][Au(C6F5) 2] versus [Pt(tpy)CCPh]PF6 ascribed to an intermolecular charge transfer. © 2010 Elsevier B.V. All rights reserved.