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Synthesis and characterization of two self-assembled [Cu6Gd3] and [Cu5Dy2] complexes exhibiting the magnetocaloric effect, slow relaxation of magnetization, and anticancer activity
Two new paths for coordination driven self-assembly reactions under the binding support of 2-((1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L) have been discovered from the reactions of Cu(ClO4)2·6H2O, NEt3 and GdCl3/DyCl3·6H2O in MeOH/CHCl3 (2 : 1) medium. A similar synthetic protocol is useful to provide two different types of self-aggregated molecular clusters [Cu6Gd3(L)3(HL)3(μ3-Cl)3(μ3-OH)6(OH)2]ClO4·4H2O (1) and [Cu5Dy2(L)2(HL)2(μ-Cl)2(μ3-OH)4(ClO4)2(H2O)6](ClO4)2·2NHEt3Cl·21H2O (2). The adopted reaction procedure established the importance of the HO− and Cl− ions in the mineral-like growth of the complexes, derived from solvents and metal ion salts. In the case of complex 1, one GdIII center has been trapped at the central position of the core upheld by six μ3-OH and three μ3-Cl groups, whereas for complex 2 one CuII center was trapped using four μ3-hydroxo and two μ-chlorido groups. The magnetothermal behavior of 1 has been examined for a magnetocaloric effect of −ΔSm = 11.3 J kg−1 K−1 at 2 K for ΔH = 7 T, whereas the magnetic susceptibility measurements of 2 showed slow magnetic relaxation with Ueff = 15.8 K and τ0 = 9.8 × 10−7 s in zero external dc field. Cancer cell growth inhibition studies proved the potential of both the complexes with interestingly high activity for the Cu6Gd3 complex against human lung cancer cells. Both complexes 1 and 2 also exhibited DNA and human serum albumin (HSA) binding abilities in relation to the involved binding sites and thermodynamics.
Author affiliationDepartment of Chemistry, University of Leicester
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