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
Journal Title
Journal ISSN
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Publisher
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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Keywords
Chemistry