Butterfly-like Heteronuclear 3d–4f Metal Clusters: Synthesis, Structures, Magnetic Properties, and Magnetocaloric Effect

This study describes the self-assembled synthesis, characterization, and structural features of two new heterometallic Fe6Ln clusters, [Fe6Ln(μ3-OH)2(mdea)6(N3)6(NO3)] (Ln = Y (1), Gd (2); mdeaH2 = N-methyldiethanolamine). The obtained compounds possess a unique crystalline structure with a vertex-sharing butterfly-like Fe3LnFe3 motif and a rare type of 2,3,4M7-1 topology. The compounds show a new prototype structure with a distinctive arrangement of a lanthanide center between the Fe3 triangles. Magnetic properties of the obtained clusters were investigated in detail. In 1, the best fit through a spin Hamiltonian to the experimental data of both magnetic susceptibility and magnetization curves gave J values ranging from −5.5 to −11.1 cm–1. In 2, these values vary from −18.0 to −31.5 cm–1. The cluster 2 also showed a magnetocaloric effect (MCE) with a −ΔSm value of 10.6 J kg–1 K–1 (16.3 J mol–1 K–1) at 2.0 K. This effect is superior to that of other metallacrown compounds (with one Gd inside of an antiferromagnetic matrix of iron centers). The obtained compounds bring a new example of heptametallic clusters into a family of heteronuclear iron(III)-lanthanide derivatives with notable structural characteristics and magnetic behavior. © 2021 American Chemical Society

Akhtar M.N.1 , AlDamen M.A.2 , Fitta M.3 , Shahid M.4 , Kirillov A.M. 5, 6
American Chemical Society
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  • 1 Division of Inorganic Chemistry, Institute of Chemistry, Baghdad-ul-Jadeed Campus, The Islamia University of Bahawalpur, Bahawalpur, 63100, Pakistan
  • 2 Department of Chemistry, School of Science, The University of Jordan, Amman, 11942, Jordan
  • 3 Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, 31-342, Poland
  • 4 Functional Inorganic Materials Laboratory (FIML), Department of Chemistry, Aligarh Muslim University, Aligarh, 202002, India
  • 5 Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon, 1049-001, Portugal
  • 6 Research Institute of Chemistry, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya st., Moscow, 117198, Russian Federation
Ключевые слова
Iron compounds; Magnetic susceptibility; Rare earth elements; Cluster synthesis; Crystalline structure; Heterometallics; Heteronuclear; Metal cluster; N-methyldiethanolamine; Prototype structures; Structural feature; Synthesis features; Vertex sharing; Magnetocaloric effects
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