Hanuza J, Godlewska P, Lisiecki R, Ryba-Romanowski W, Kadłubański P, Lorenc J, Łukowiak A, Macalik L, Gerasymchuk Yu, Legendziewicz J
Institute of Low Temperature and Structure Research, 2 Okólna str., 50-422 Wrocław, Poland.
Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology, Faculty of Engineering and Economy, Wrocław University of Economics, Poland.
Spectrochim Acta A Mol Biomol Spectrosc. 2018 May 5;196:202-208. doi: 10.1016/j.saa.2018.01.003. Epub 2018 Jan 4.
The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln=Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass.
测量了固态及共掺杂在石英玻璃中的金字塔形LnPc(OAc)配合物（其中Ln = Er、Eu和Ho）的电子吸收光谱和发射光谱。使用四种近似方法CAM - B3LYP/LANL2DZ、CAM - B3LYP/CC - PVDZ、B3LYP/LANL2DZ和B3LYP/CC - PVDZ通过量子化学DFT计算确定了理论电子光谱。结果表明，对于CAM - B3LYP/LANL2DZ模型，计算得到的结构参数和光谱数据与实验结果之间的吻合度最佳。使用配体和镧系元素吸收范围内的激发光测量了发射光谱。讨论了酞菁配体与镧系离子激发态之间能量转移的可能性。结果表明，从金属态到酞菁态的反向能量转移是所研究配合物在多晶态和石英玻璃中观察到的发射的原因。
