Electronic structure and optical properties of Eu(III) tris-β-diketonate adducts with 1,10-phenanthroline

Shurygin, A. V.; Korochentsev, V. V.; Cherednichenko, A. I.; Мирочник, А. Г.; Kalinovskaya, I. V.; Vovna, V. I.

doi:10.1016/j.molstruc.2017.10.110

Cited by 13 publications

(6 citation statements)

References 21 publications

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“…In many cases, it is not possible to match the calculated and experimental bands on a 1:1 basis. The PBE0 functional has been shown to out-perform others in the calculation of absorption spectra of organic molecules, , and it has been the chosen functional in many studies of lanthanide complexes. ,, The parameters in our TD-DFT calculations have been optimized, and the basis set employed is superior to others employed in our preliminary calculations. The differences in simulation of Figure a–d mainly arise from the very different method of calculation of the excited state spectrum: namely, TD-DFT and the semiemipirical ZINDO/S method.…”

Section: Comparison Of the Absorption Spectra With Those Calculated U...mentioning

confidence: 99%

“…The PBE0 functional has been shown to out-perform others in the calculation of absorption spectra of organic molecules, 23,77 and it has been the chosen functional in many studies of lanthanide complexes. 17,27,28 The parameters in our TD-DFT calculations Refer to the text for explanation of TD-DFT and ΔSCF Calculations. Underlined energies are from CASSCF and NEVPT2 calculations, as indicated.…”

Section: ■ Comparison Of the Absorption Spectra With Those Calculated...mentioning

confidence: 99%

“…Calculations employing relativistically recontracted Karlsruhe (Douglas–Kroll–Hess – DKH or zero-order regular approximation for relativistic effects – ZORA) basis sets , with segmented all-electron relativistically contracted basis sets or atomic natural orbital basis sets are often impracticable for sets of lanthanide complexes because of the immense time required. Hence, many time dependent–density functional theory (TD-DFT) calculations − have been attempted on lanthanide ion complexes using effective core potentials (ECPs), which place the electronic ground state as a 4f N configuration (for example, a high spin septet for Eu 3+ using the Stuttgart group ECP 28MWB , or as a closed shell: 52MWB for Eu 3+ ) . In the latter case, the intra-4f N energy levels of Eu 3+ are not considered and only the relevant ligand levels in the complex are calculated.…”

Section: Introductionmentioning

confidence: 99%

“…In the latter case, the intra-4f N energy levels of Eu 3+ are not considered and only the relevant ligand levels in the complex are calculated. Several studies have reported that calculations of lanthanide complexes using the PBE0-D3/6–31+G(d) level − (or simply Becke, 3-parameter, Lee–Yang–Parr/B3LYP level) of calculation with an appropriate ECP are economical and reasonably accurate. ,− The PBE0 functional is based on the generalized gradient approximation and contains the fixed fraction of 25% exact exchange. Hence, as a start, we have also employed the large-core ECPs in our calculations for lanthanide ion complexes with the PBE0 functional and appropriate basis sets.…”

Section: Introductionmentioning

confidence: 99%

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Determination of Triplet State Energy and the Absorption Spectrum for a Lanthanide Complex

et al. 2021

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The usual depiction of energy transfer from an antenna of a lanthanide complex, LnL n , to the lanthanide ion, Ln3+, such as Eu3+ or Tb3+, is illustrated by an energy diagram matching the complex and metal ion levels. Other than direct singlet energy transfer (ET), relaxation to the lowest triplet state, T1, may be followed by ET. The determination of the zero phonon line triplet state energy, T1, is thus essential for the rationalization of the ET processes of lanthanide ions. It is also useful to calculate the electronic absorption spectra of lanthanide complexes to pinpoint maximum absorption. The triplet state energy and the energies of absorption bands have not been thoroughly investigated by calculation and compared with experimental results in a critical manner previously. In order to study and provide guidelines on these points, we have made an experimental and theoretical investigation of the energy levels of lanthanide complexes in the solid state and in solution by employing well-characterized compounds. It is found that time dependent–density functional theory (TD-DFT) methods do not provide a good indication of the complex absorption spectrum, but reasonable agreement is achieved from multireference methods or more rapidly from the Zerner’s intermediate neglect of differential overlap (ZINDO/S) semiempirical method for calculating excited states. Although the absorption spectra of the complexes may be similar for different lanthanide ions and may be fairly similar to those of the ligands, the use of a fragment scheme to calculate absorption spectra using TD-DFT is generally not accurate. The major absorption bands correspond to higher energy singlet transitions and the energies of the first singlet and triplet states are not well-predicted by the above methods. The calculation of the triplet zero phonon line energy is best performed by the correction of the adiabatic transition energy by the difference in the zero-point vibrational energy of the ground singlet (S0) and the triplet (T1) states: the ΔSCF (self-consistent field) method. The geometry optimization of the complex in each electronic state followed by confirmatory vibrational frequency calculations is thus required. This study lays down the platform for a more accurate description and understanding of the ET processes of lanthanide ions in organic complexes.

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Section: Comparison Of the Absorption Spectra With Those Calculated U...mentioning

confidence: 99%

Section: ■ Comparison Of the Absorption Spectra With Those Calculated...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Determination of Triplet State Energy and the Absorption Spectrum for a Lanthanide Complex

et al. 2021

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“…As is well known, the fluorescent materials are able to absorb the short-wavelength photons and convert them into longwavelength photons with better spectral responsiveness for solar cells [11][12][13]. Proceeding from this angle, rare-earth europium complexes can be introduced into solar cells with a significant impact on the photoelectric conversion efficiency [14][15][16][17]. Consequently, the optical conversion materials are capable of absorbing UV radiation effectively, which are worthy of further research and development.…”

Section: Introductionmentioning

confidence: 99%

Multiligand Europium Complexes Incorporated Polyvinylpyrrolidone for Enhanced Solar Cell

Guo

et al. 2019

Advances in Materials Science and Engineering

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Intense reddish-orange fluorescence of Eu3+ is observed in multiligand europium complexes Eu(BA)(TTA)2 and Eu(BA)(TTA)2Phen doped polyvinylpyrrolidone (PVP). Under 367 nm UVA-LED pumping with 708.5 μW, the net emission powers are as high as 204.8 and 243.2 μW, and the total emission photon numbers are derived to be 635.9 × 1012 and 754.9 × 1012 cps for Eu(BA)(TTA)2 and Eu(BA)(TTA)2Phen doped PVP thin films, respectively. It is incredible that the quantum yield (QY) is up to 57.87% in the former; furthermore, as the introduction of Phen, the QY of Eu3+ is increased to 62.03%, verifying the effectiveness of multiligands in photon conversion. Conclusive photon quantification and efficient fluorescence emission reveal the potential of europium complexes/PVP as UV-visible conversion layers for enhanced solar cells.

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β-Diketones: Coordination and Application

Crossman¹,

Marshak²

2021

Comprehensive Coordination Chemistry III

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Electronic structure and optical properties of Eu(III) tris-β-diketonate adducts with 1,10-phenanthroline

Cited by 13 publications

References 21 publications

Determination of Triplet State Energy and the Absorption Spectrum for a Lanthanide Complex

Determination of Triplet State Energy and the Absorption Spectrum for a Lanthanide Complex

Multiligand Europium Complexes Incorporated Polyvinylpyrrolidone for Enhanced Solar Cell

β-Diketones: Coordination and Application

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