Syntheses, crystal structures, and solid-state photoluminescence properties of heterotrinuclear Zn2Ln (Ln: La, Sm, Eu, Tb) complexes derived from 1,4-DIAMINOBUTANE (cas 110-60-1)-based N2O4 compartmental ligand

Add time:08/21/2019    Source:sciencedirect.com

The one-pot reaction of N,N′-bis(3-methoxysalicylidene)-1,4-diaminobutane (MeOsalbnH2), zinc(II) perchlorate, and lanthanide(III) acetate by a molar ratio of 2:2:1 affords a heterotrinuclear Zn2Ln (Ln: La, Sm, Eu, Tb) complex formulated as [Ln(CH3COO)2{Zn(MeOsalbn)}2]ClO4. In this complex, the central Ln(III) atom is bridged by two {Zn(MeOsalbn)} units and two acetate ligands to form ten-coordination environment. Each Zn(II) atom is coordinated by MeOsalbn2− through the N2O2 site and one oxygen atom from the bridging acetate to afford a five-coordination geometry. In the crystalline state at room temperature, the La(III) complex exhibits a bright blue fluorescence, while the Sm(III) complex shows a reddish-orange colored f–f photoluminescence via an energy transfer from the T1 state localized on the {Zn(MeOsalbn)} units to the acceptor level of the central Sm(III) ion. The results of TD-DFT calculations show that the lowest excited singlet state or triplet state involved in photoluminescence of the La(III) or Sm(III) complex has some intramolecular charge-transfer (CT) character from the phenoxo or methoxy groups to the imino groups in the coordinated MeOsalbn2− moieties.

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