Synthesis, Crystal Structures And Photoluminescence Studies Of Metal Complexes Containing Ligands Derived From Diels-Alder Adduct

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Date
2021-03
Authors
Azmi, Nurul Izzati
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Universiti Sains Malaysia
Abstract
A condensation reaction between the Diels-Alder adducts of anthracene and maleic anhydride with 𝛽-alanine and 3-aminobenzoic acid, facilitates the formation of new compounds, namely N-3-(9,10-dihydroanthracene-11,12- dicarboximide)propanoic acid (HL1) and N-3-(9,10-dihydroanthracene-11,12- dicarboximide)benzoic acid (HL2), respectively. A one pot-reaction of HL1 with copper(II) acetate afforded the formation of mononuclear complex, [CuL1(H2O)3] (1). By leaving the blue crystal of 1 in high concentrated methanolic vapor resulting the formation of pale green crystal of dinuclear complex, [Cu2(μ- L1)4(MeOH)(H2O)] (2). This observation indicated the solvent-vapor mediated single-crystal-to-single-crystal (SCSC) transformation that promoted nuclearity cross-over from mononuclear to dinuclear of Cu(II) complex. This phenomenon due to the removal/exchange of water/solvent molecules and subsequent structural rearrangement in the crystalline phase. By undertaking hydrothermal synthesis reaction of HL2 and copper(II) acetate, dinuclear complex [Cu2(μ-L2)4(H2O)2] (3) was obtained, in which the structural arrangement is almost similar to 2, with coordinated of water in 3 instead of methanol. The reaction of HL1 and nickel(II) acetate resulted the formation of 1-D coordination polymer, [Ni(L1)2(μ- H2O)2(H2O)2]n·nH2O (4). Meanwhile, both reaction between silver(I) acetate with HL1 and HL2 allowed the formation of dinuclear complexes [Ag2(μ-L1)2(H2O)2] (5) and [Ag2(μ-L2)2(H2O)2] (6), respectively. Unexpectedly, the reaction between silver(I) acetate, HL2 and 4,4’-bipyridine formed a complex [Ag(𝜇-L2)(4,4-bpy)]n (7) as 1-D polymeric structure with the central silver(I) ions display unprecedented square-planar geometry, which is outlier from common tetrahedral geometry of d10 system. Besides, the reaction of terbium(III) nitrate pentahydrate with HL1 and HL2, lead the formation of dinuclear cluster for both lanthanide complexes, [Tb2(μ- L1)2(L1)4(H2O)4(MeOH)2] (8) and [Tb2(μ-L2)2(L2)4(H2O)2(MeOH)2] (9), respectively. Remarkably, in the photoluminescence studies, complex 5 reveals that this dinuclear has potential as a ratiometric luminescent temperature sensor that features dual emission property with emission maxima at 415 and 550 nm. In contrast to 5, both complexes 6 and 7 only appeared a mono emission characteristic at ~420 nm due to the absence of intermetallic argentophilic interactions in these complexes. On the other side, both complexes 8 and 9 also display fascinating photoluminescence property with the highest fluorescence intensity emission peak at 545 nm that resulted in green emission.
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Chemistry
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