Diagnostic Organometallic and Metallodendritic Materials for SO2 Gas Detection : Reversible Binding of Sulfur Dioxide to Arylplatinum(II) Complexes

Abstract

series of square-planar platinum(II) complexes of the N,C,N-terdentate-coordinating monoanionic pincer ligand, [PtX(4-E-2,6-{CH2NRR}2-C6H2)] (X=Cl, Br, I, tolyl; R, R=Et, Me; E=H, OH, OSiMe2tBu) has been prepared. In the presence of sulfur dioxide, these complexes spontaneously adsorb this gas to form pentacoordinated adducts. Solid-state crystal-structure analyses of the SO2 adducts 8 c (X=I, R=R=Me, E=OSiMe2tBu) and 11 (X=Cl, R=R=Me, E=OH) show a square-pyramidal geometry around the metal center with SO2 in the apical position. Most interestingly, the adduct 11 forms similar Pt-ClH-O hydrogen-bonded -type networks as the corresponding SO2-free complex 5. The conservation of the supramolecular information (hydrogen-bonded self-assembly) throughout a reaction (SO2 adsorption) is unprecedented in crystal engineering. Adduct formation in the solid state or in solution is fast and reversible and is indicated by a characteristic color change of the material from colorless to bright orange. Since facile methods have been developed to remove SO2 from the adducts and to regenerate the square-planar starting complexes, these complexes fulfill several essential prerequisites of sensor materials for repeated diagnostic SO2 detection. The platinum sensors have been found to be highly selective for sulfur dioxide and particularly sensitive for submilimolar to molar gas quantities. Their response capacity is tuneable by electronic and steric modifications of the ligand array by introduction of, for example, different substituents on the nitrogen donors. The periphery of dendrimers is shown to be an appropriate macromolecular support for anchoring the detection-active sites, thus allowing full recovery of the sensor materials for repeated use. By using this concept, metallo-dendrimers 3 and 15 have been prepared. Owing to the dendritic connectivity, these sensors are suitable for repetitive qualitative and quantitative detection of small amounts of SO2.