| Summary: | 碩士 === 國立中正大學 === 化學暨生物化學研究所 === 107 === In this thesis, we used (aza-15-crown-5)bis(dithiocarbamate) (C18NO4(CS2)) and (aza-18-crown-6)bis(dithiocarbamate) (C18NO5(CS2)) to react with [(μ-Cl)Pt(C^N-2-Phpy)]2 or Pt(N^N)Cl2 (N^N=2,2´-bipyridine) respectively to give a series of mononuclear metal complexes 1-3 and one 2-D coordination polymer 4, which have been isolated and structurally characterized by X-ray diffraction studies. Complex 2 with the Pt(II) ion at a square-planar coordination environment having a close Pt...Ptinter contact of 3.5361Å forms a one-dimensional supramolecular structure. Complex 4 also shows a similar coordination environment, whereas it forms a one-dimensional coordination polymer through coordination between the encapsulated sodium ion in an azacrown ether ring and the perchlorate anion. There are two kinds of close Pt...Ptintra (3.4018 Å) and Pt...Ptinter (3.8474 Å) contacts. However, no close Pt...Ptinter contact has been observed for complexes 1 and 3.
To investigate the solvent-induced luminescence the mechanical grinding of 1-4 with various solvents was carried out. Surprisingly, the grinding process for complex 4 with addition of nitrobenzene is the only example to cause a significant blue shift for the luminescence energy. We reason that upon grinding the Nitrobenzene molecule is expected to enter crystal lattices and to lengthen the Pt...Ptinter contacts. Other solvent molecules cannot show similar effects. Therefore, we believe that complex 4 can show a selective detection toward Nitrobenzene.
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