Synthesis and photoelectronic properties on a series of lanthanide dysprosium(III) complexes with acetylacetonate and meso-tetraalkyltetrabenzoporphyrin

摘要

Lanthanide dysprosium(III) complexes with acetylacetonate and meso-tetraalkyltetrabenzoporphyrin (TATBP) having the general formula Dy(TATBP)acac (where A=alkyl=C_6H_(13), C_8H_(17), C_(10)H_(21), C_(12)H_(25), C_(14)H_(29), C_(16)H_(33) and C_(18)H_(37); Hacac=acetylacetone) are reported. (The structures of ligand and complexes were shown in Fig. 1(a) tetraalkyltetrabenzoporphyrin, TATBP, n=5, 7, 9, 11, 13, 15, 17 correspond to 6L, 8L, 10L, 12L, 14L, 16L and 18L, respectively. Fig. 1(b) lanthanide(III) complexes with acetylacetonate and meso-tetraalkyltetrabenzoporphyrin, Dy(TATBP)acac, n=5, 7, 9, 11, 13, 15, 17 correspond to 6Dy, 8Dy, 10Dy, 12Dy, 14Dy, 16Dy and 18Dy, respectively.) These compexes have been studied by elemental analyses, UV–vis spectra, infrared spectra, molar conductance, ~1H NMR spectra, cyclic voltammetry, surface photovoltage spectroscopy (SPS) and luminescenc spectroscopy. The infrared spectral bands of the ligand and complexes were assigned. In dimethylformamide (DMF), 0.1 M tetrabutylammonium perchlorate (TBAP), the synthesized TATBP exhibit two one-electron reversible redox reactions and Dy(TATBP)acac show three redox reactions, respectively, within the accessible potential window of the solvent and the measured electrochemical redox potentials. The absorption bands of the complexes appear in the range 431–434 (Soret band), 578–581 (Q band) and 629–630 nm (Q band). The photovoltaic properties and charge transfer process of these compounds were investigated by surface photovoltage spectroscopy (SPS), which reveal that these ligands and complexes are all p-type semiconductor. Quantum yields of the S_1→S_0 fluorescence are in the region 0.26–0.28 and the fluorescence lifetimes are in the region 0.013–0.019 ms at room temperature. The phosphorescence bands of the complex at 77 K appears 714 nm. It is found that the stronger the fluorescence intensity is, the weaker the surface photovoltage intensity is.