Lanthanide coordination compounds of the formula Na[Ln(L)4](1 Ln),where Ln=La^3+,Eu^3+,Gd^3+,Tb^3+,L=[L]-and HL=dimethyl(4-methylphenylsulfo nyl)amidophosphate,were synthesized.Their structural and spectro scopic prop...Lanthanide coordination compounds of the formula Na[Ln(L)4](1 Ln),where Ln=La^3+,Eu^3+,Gd^3+,Tb^3+,L=[L]-and HL=dimethyl(4-methylphenylsulfo nyl)amidophosphate,were synthesized.Their structural and spectro scopic properties were discussed in detail based on X-ray diffraction measurements,IR spectroscopy,absorption and emission spectroscopy at 293 and 77 K and theoretical calculations of the intramolecular energy transfer(IET)rates.DFT calculations were used to investigate the 1 Ln electronic properties re quired to calculate the transition rates.30 and 22 pathways of intramolecular nonradiative energy transfer were examined in the case of 1 Eu and 1 Tb,respectively.It is shown that the main pathway for sensitization of the lanthanide emission is either the triplet(1 Eu)or singlet(1 Tb)transfer,occurring mainly through the exchange mechanism.The energy rates for energy transfer from S1 and T1 equal WS=1.53×10^5 s^-1(1 Eu),WT=5.14×10^6 s^-1(1 Eu)and WS=4.09×10^7 s^-1(1 Tb),WT=6.88×10^5 s^-1(1 Tb).The crucial role of the 7 F5 level in the energy transfer process of 1 Tb and the participation of the LMCT state in the depopulation of the ligand singlet state of 1 Eu were demonstrated.The influence of the resonance effect on the splitting of the7 F1 level in 1 Eu was analyzed.By comparing the properties of 1 Ln with the properties of 2 Ln coordination compounds,sharing the same ligand and crystallizing in the same crystallographic system(monoclinic),but with a different space group,it is demonstrated how slight structural changes can affect the photophysical properties of Ln compounds.展开更多
基金Project supported by the Minister of Science and Higher Education POIG.01.01.02-02-006/09the grant Minister of Science and Higher Education for young scientists 2432/M/WCH/14+1 种基金partially developed within the scope of the project CICECO-Aveiro Institute of Materials,FCT(Portuguese agency)Ref.UID/CTM/50011/2019financed by national funds through the FCT/MCTES。
文摘Lanthanide coordination compounds of the formula Na[Ln(L)4](1 Ln),where Ln=La^3+,Eu^3+,Gd^3+,Tb^3+,L=[L]-and HL=dimethyl(4-methylphenylsulfo nyl)amidophosphate,were synthesized.Their structural and spectro scopic properties were discussed in detail based on X-ray diffraction measurements,IR spectroscopy,absorption and emission spectroscopy at 293 and 77 K and theoretical calculations of the intramolecular energy transfer(IET)rates.DFT calculations were used to investigate the 1 Ln electronic properties re quired to calculate the transition rates.30 and 22 pathways of intramolecular nonradiative energy transfer were examined in the case of 1 Eu and 1 Tb,respectively.It is shown that the main pathway for sensitization of the lanthanide emission is either the triplet(1 Eu)or singlet(1 Tb)transfer,occurring mainly through the exchange mechanism.The energy rates for energy transfer from S1 and T1 equal WS=1.53×10^5 s^-1(1 Eu),WT=5.14×10^6 s^-1(1 Eu)and WS=4.09×10^7 s^-1(1 Tb),WT=6.88×10^5 s^-1(1 Tb).The crucial role of the 7 F5 level in the energy transfer process of 1 Tb and the participation of the LMCT state in the depopulation of the ligand singlet state of 1 Eu were demonstrated.The influence of the resonance effect on the splitting of the7 F1 level in 1 Eu was analyzed.By comparing the properties of 1 Ln with the properties of 2 Ln coordination compounds,sharing the same ligand and crystallizing in the same crystallographic system(monoclinic),but with a different space group,it is demonstrated how slight structural changes can affect the photophysical properties of Ln compounds.
