AI Article Synopsis

  • The odd-even effect was observed in luminescent Eu complexes with various dicarboxylate ligands for the first time, demonstrating a unique relationship between the molecular structure and luminescent properties.
  • The dehydration temperatures of these complexes exhibited a zigzag pattern based on the carbon chain length of the ligands, showcasing the odd-even effect.
  • The paper introduces the ghost-atom model to explain changes in luminescence intensity parameters and discusses how water molecules impact the luminescence of these complexes.

Article Abstract

The odd-even effect in luminescent [Eu (L) (H O) ]⋅y(H O) complexes with aliphatic dicarboxylate ligands (L: OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND, and DOD, where x=2-6 and y=0-4), prepared by the precipitation method, was observed for the first time in lanthanide compounds. The final dehydration temperatures of the Eu complexes show a zigzag pattern as a function of the carbon chain length of the dicarboxylate ligands, leading to the so-called odd-even effect. The FTIR data confirm the ligand-metal coordination via the mixed mode of bridge-chelate coordination, except for the Eu -oxalate complex. XRD results indicate that the highly crystalline materials belong to the monoclinic system. The odd-even effect on the 4 f-4 f luminescence intensity parameters (Ω and Ω ) is explained by using an extension of the dynamic coupling mechanism, herein named the ghost-atom model. In this method, the long-range polarizabilities ( ) were simulated by a ghost atom located at the middle of each ligand chain. The values of were estimated using the localized molecular orbital approach. The emission intrinsic quantum yield ( ) of the Eu complexes also presented an the odd-even effect, successfully explained in terms of the zigzag behavior shown by the Ω and Ω intensity parameters. Luminescence quenching due to water molecules in the first coordination sphere is also discussed and rationalized.

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http://dx.doi.org/10.1002/cphc.201900603DOI Listing

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