Details

Autor(en) / Beteiligte

• Pollock, J. Bryant
• Cook, Timothy R
• Stang, Peter J

Titel

Photophysical and Computational Investigations of Bis(phosphine) Organoplatinum(II) Metallacycles

Ist Teil von

• Journal of the American Chemical Society, 2012-06, Vol.134 (25), p.10607-10620

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2012

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A series of endohedral and exohedral amine-functionalized ligands were synthesized and used in the construction of supramolecular D 2h rhomboids and a D 6h hexagon. These supramolecular polygons were obtained via self-assembly of 120° dipyridyl donors with 180° or 120° diplatinum precursors when combined in 1:1 ratios. Steady-state absorption and emission spectra were collected for each ligand and metallacycle. Density functional theory (DFT) and time-dependent DFT calculations were employed to probe the nature of the observed optical transitions for the rhomboids. The emissive properties of these bis­(phosphine) organoplatinum metallacycles arise from ligand-centered transitions involving π-type molecular orbitals with modest contributions from metal-based atomic orbitals. The D 2h rhomboid self-assembled from 2,6-bis­(4-pyridylethynyl)­aniline and a 60° organoplatinum­(II) acceptor has a low-energy excited state in the visible region and emits above 500 nm, properties which greatly differ from those of the parent 2,6-bis­(4-pyridylethynyl)­aniline ligand.