Zinc Vice Family Of Divalent Ions On Structure And Spectroscopic Properties Of Theoretical Research,

In designing luminescent materials with transition metal complexes, theoretical investigation has been paid much attention to because of its accurate predication on electronic spectroscopy and lower cost than experimental study. In the thesis, structures in ground and excited states and spectroscopic properties of metal(II) complexes coordinated by the C, N and S ligands were explored using ab initio, density functional theory (DFT) and time-dependent DFT methods; relativistic effects of heavy metal were taken into account in the calculations, and solvent effects were simulated by polarized continuum model. It was shown that the featured absorptions and emissions were attributed to the intraligand charge transfer (ILCT) modified by metal. In fluorenone-alkynyl Hg(II) complexes with the C-M bonding,π→π* transition contributes to the ILCT, while one additional n→π* in other metal(II) complexes with the N/S-M bonds. Increasing ligand number, modifying ligand chemically and varying metal ions could tune the transition energy of spectral band, but do not change the transition nature. The calculations revealed that the bright fluorescent materials from organic compound can be converted into the bright phosphorescent materials from organometallic complexes via heavy metal modification. These organometallic complexes should bear characteristics of both organic and inorganic luminescent materials.