Complexation and extraction of PAHs to the aqueous phase with a dinuclear PtII diazapyrenium-based metallacycle

Abstract

New palladium and platinum metallacycles have been synthesized by reaction between a 2,7-diazapyrenium-based ligand and PdII and PtII complexes. The inclusion complexes between the metallacycles and polycyclic aromatic hydrocarbons (PAHs) in CD3NO2 and D2O were studied by NMR spectroscopy. The structures of the inclusion complexes of the Pt metallacycle as host with pyrene, phenanthrene, and triphenylene were confirmed by single crystal X-ray crystallography. The association constants between the Pt metallacycle and the selected PAHs were determined in CH 3CN following the characteristic charge-transfer band displayed in their UV/Vis absorption spectrum. Although in aqueous solution all the complexes showed a 1:1 stoichiometry, in CH3CN the Job plot indicated a 2:1 stoichiometry for complexes with triphenylene and benzo[a]pyrene. The estimated association constants in water correlate with the hydrophobicity of the PAH, indicating that hydrophobic forces play an important role in the complexation process. SuPAH extraction! New metallacycles have been synthesized by self-assembly between a 2,7′-diazapyrenium-based ligand and Pd II and PtII complexes. The inclusion complexes between the metallacycles and polycyclic aromatic hydrocarbons (PAHs) in CD3CN and D2O were studied. The structures of complexes with pyrene, phenanthrene, and triphenylene were confirmed by single-crystal X-ray crystallography (see graphic). The estimated association constants in water correlate with the hydrophobicity of the PAH. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.