Chiral-at-Metal Phosphorescent Square-Planar Pt(II)-Complexes from an Achiral Organometallic Ligand.
Thorben R SchulteJulian J HolsteinLennard KrauseReent MichelDietmar StalkeEri SakudaKeisuke UmakoshiGiovanna LonghiSergio AbbateGuido H CleverPublished in: Journal of the American Chemical Society (2017)
The synthesis and characterization of a new kind of cis- and trans-cyclometalated square-planar platinum(II) complexes is reported. Uncharged organometallic compounds carrying one or two of the C∧N-donor ligand LCN were prepared. Due to the heterobidentate coordination of the achiral chelate ligand, the formed [PtLCNCl(SEt2)], cis- and trans-[PtLCN2] complexes are chiral with the metal serving as the stereo center. The enantiomers of complex trans-[PtLCN2] could be separated and their absolute configuration was determined by anomalous X-ray diffraction, in accordance with CD spectroscopic results and TD-DFT calculations. All compounds were fully characterized by NMR spectroscopy, mass spectrometry and X-ray structure determination. The photophysical properties of trans-[PtLCN2] have been investigated showing phosphorescence in solution and in the solid state with a moderate quantum yield. For the enantiomers, strong circular dichroism (CD) and circularly polarized luminescence (CPL) effects were observed, rendering this new structural motif suitable for application in chiroptical and luminescent materials.
Keyphrases
- capillary electrophoresis
- solid state
- mass spectrometry
- high resolution
- molecular dynamics
- molecular docking
- density functional theory
- quantum dots
- energy transfer
- liquid chromatography
- electron microscopy
- dual energy
- molecular dynamics simulations
- room temperature
- magnetic resonance imaging
- nk cells
- computed tomography
- crystal structure
- high intensity
- gas chromatography
- contrast enhanced
- high speed