Theoretical investigation on the structures of the octacoordinated [Nd(CO3)4]5-and the nonacoordinated [Nd(CO3)4.OH2]5-complexes, using the SPARKLE parameters of the lanthanides within MOPAC, revealed that they posses...Theoretical investigation on the structures of the octacoordinated [Nd(CO3)4]5-and the nonacoordinated [Nd(CO3)4.OH2]5-complexes, using the SPARKLE parameters of the lanthanides within MOPAC, revealed that they possessed dodecahedral and square antiprismatic structures respectively with an average Nd-O distance of 0.249 nm. These structures and the Nd-O distances agreed well with those experimentally found in the crystal structures. Replacing the water molecule with a fluoride ion or a mondentatecarbonato ligand resulted in a nonacoordinated distorted square antiprismatic structures where the trans-carbonato groups were twisted. The corresponding decacoordinated structures with two fluoride ions or a bidentatecarbonato group, [Nd(CO3)4·F2]7-and [Nd(CO3)5]7-, were also investigated. In both cases considerable twisting of the transcarbonato groups was observed.展开更多
The title complexes were modeled using the semiempirical MOPAC and the newly developed SPARKLE paramerters of the lanthanides. The calculated bond dis tances and angles agreed well with those found from crystal struct...The title complexes were modeled using the semiempirical MOPAC and the newly developed SPARKLE paramerters of the lanthanides. The calculated bond dis tances and angles agreed well with those found from crystal structure measuremen ts. This technique allows us to screen a large number of molecules and get struc tural information within a very short time.展开更多
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
A rovibrational model,including anharmonic,centrifugal,and Coriolis corrections,is used to calculate π,K,N,and ∑ orbital and radial resonances.The four orbital excitations of the n meson correspond to the/?(1235),ti...A rovibrational model,including anharmonic,centrifugal,and Coriolis corrections,is used to calculate π,K,N,and ∑ orbital and radial resonances.The four orbital excitations of the n meson correspond to the/?(1235),ti2(1670),63(2030),and π4(2250)resonances.Its first four radial excitations correspond to the π(1300),π(1800),π(2070),and 7t(2360)resonances.The orbital excitations of the K meson are interpreted as the K_(1)(1270),K_(2)(1770),K_(3)(2320),and K_(4)(2500)resonances;its radial excitations correspond to the K(1460)and K(1830)resonances.The N orbital excitations are identified with the N(1520),N(1680),N(2190),N(2220),and N(2600)resonances.The first four radial excitations of the N family correspond to the N(1440),N(1880),N(2100),and N(2300)resonances.The orbital excitations of the ∑ baryon are associated with the ∑(1670),∑(1915),∑(2100),and ∑(2250)resonances,whereas its radial excitations are identified with the ∑(1660),∑(1770),and ∑(1880)resonances.The proposed rovibrational model calculations show a good agreement with the corresponding experimental values and allow for the prediction of hadron resonances,thereby proving to be useful for the interpretation of excited hadron spectra.展开更多
文摘Theoretical investigation on the structures of the octacoordinated [Nd(CO3)4]5-and the nonacoordinated [Nd(CO3)4.OH2]5-complexes, using the SPARKLE parameters of the lanthanides within MOPAC, revealed that they possessed dodecahedral and square antiprismatic structures respectively with an average Nd-O distance of 0.249 nm. These structures and the Nd-O distances agreed well with those experimentally found in the crystal structures. Replacing the water molecule with a fluoride ion or a mondentatecarbonato ligand resulted in a nonacoordinated distorted square antiprismatic structures where the trans-carbonato groups were twisted. The corresponding decacoordinated structures with two fluoride ions or a bidentatecarbonato group, [Nd(CO3)4·F2]7-and [Nd(CO3)5]7-, were also investigated. In both cases considerable twisting of the transcarbonato groups was observed.
文摘The title complexes were modeled using the semiempirical MOPAC and the newly developed SPARKLE paramerters of the lanthanides. The calculated bond dis tances and angles agreed well with those found from crystal structure measuremen ts. This technique allows us to screen a large number of molecules and get struc tural information within a very short time.
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.
基金Supported by the Brazilian funding agencies CNPq-Conselho Nacional de Desenvolvimento Cientifico e Tecnologico and CAPES-Coordenapao de Aperfeicoamento de Pessoal de Nivel Superior。
文摘A rovibrational model,including anharmonic,centrifugal,and Coriolis corrections,is used to calculate π,K,N,and ∑ orbital and radial resonances.The four orbital excitations of the n meson correspond to the/?(1235),ti2(1670),63(2030),and π4(2250)resonances.Its first four radial excitations correspond to the π(1300),π(1800),π(2070),and 7t(2360)resonances.The orbital excitations of the K meson are interpreted as the K_(1)(1270),K_(2)(1770),K_(3)(2320),and K_(4)(2500)resonances;its radial excitations correspond to the K(1460)and K(1830)resonances.The N orbital excitations are identified with the N(1520),N(1680),N(2190),N(2220),and N(2600)resonances.The first four radial excitations of the N family correspond to the N(1440),N(1880),N(2100),and N(2300)resonances.The orbital excitations of the ∑ baryon are associated with the ∑(1670),∑(1915),∑(2100),and ∑(2250)resonances,whereas its radial excitations are identified with the ∑(1660),∑(1770),and ∑(1880)resonances.The proposed rovibrational model calculations show a good agreement with the corresponding experimental values and allow for the prediction of hadron resonances,thereby proving to be useful for the interpretation of excited hadron spectra.
