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Synthesis, X-ray crystal structure and photophysics of butterfly shape orange and red emanating polynuclear complexes of tris(dibenzoylmethanato)Ln(III) (Ln = Sm/Eu) and exo-bidentate 4,4'-bipyridine.
Photochemical & Photobiological Sciences 2024 January 24
Reaction of two equivalents of [Ln(dbm)3 (H2 O)] (Ln = Sm/Eu/Gd) with one equivalent of 4,4'-bipyridine (4,4'-bpy) led to the formation of rare polynuclear complexes of the type [Ln(dbm)3 (4,4'-bpy)]n (dbm is the anion of 1,3-diphenyl-1,3-propanedione) instead of symmetrically bridged dinuclear complexes. The structure of the complexes has been established by the single crystal X-ray diffraction (SC-XRD) method and shows that the coordination sphere is composed of a LnO6 N2 core (octacoordinated). Shape analysis further revealed that the geometry around Ln(III) is distorted square anti-prismatic with SHAPE value 0.738 and 25.719 for [Sm(dbm)3 (4,4'-bpy)]n and [Eu(dbm)3 (4,4'-bpy)]n , respectively. Photoluminescence (PL) properties of [Sm(dbm)3 (4,4'-bpy)]n and [Eu(dbm)3 (4,4'-bpy)]n are discussed in the solid-state and PMMA hybrid film (w/w 6%). By employing theoretical modelling in conjunction with the experimental PL data and crystal structure and an energy transfer (ET) mechanism for the sensitized PL of [Eu(dbm)3 (4,4'-bpy)]n is proposed and discussed in detail. Finally, the role of each ligand in sensitized PL of [Eu(dbm)3 (4,4'-bpy)]n is calculated and discussed by the chemical partitions of the radiative decay.Graphical abstract.
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