Synthesis and characterization of two self-assembled [Cu6Gd3] and [Cu5Dy2] complexes exhibiting the magnetocaloric effect, slow relaxation of magnetization, and anticancer activity

Abstract

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 Gd^III 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 Cu^II 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 −ΔS_m = 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 U_eff = 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.