Heterometallic (3d-4f) Coordination Clusters with Unique Topology: Self-Assembly Synthesis, Structural Features, and Magnetic Properties

Three heterometallic Fe6Ln4 clusters were self-assembled by using N-methyldiethanolamine (H2mdea) and 3,5-dinitrobenzoic acid (Hdnbz) as principal building blocks and azide as an ancillary ligand. The obtained products 1-3 were isolated as air-stable microcrystalline solids and fully characterized. Single-crystal X-ray diffraction studies reveal similar type of molecular units [Fe6Ln4(μ4-O)2(μ3-OH)2(mdea)6(dnbz)8(N3)4]·2MeCN·xH2O·CH2Cl2 {Ln = Y (1), Gd (2), Dy (3); x = 4, 6, 10, respectively}. Topological analysis of 1-3 was performed following a method for high nuclearity coordination clusters. The [Fe6Ln4(μ-O)10(μ3-O)4(μ4-O)2] cores were identified in all structures and further simplified to graph topological skeletons, which were classified as pentanodal 2,3,3,5,6-connected motifs with the unique topology. The magnetic behavior of 1-3 was investigated in detail. The magnetic studies and magnetocaloric measurements reveal that the tetranuclear gadolinium centers of 2 exhibit a high cryogenic magnetocaloric effect (MCE) that reaches 13.66 J·kg-1·K-1 (25.18 mJ·cm-3·K-1) for ΔH = 90 kOe at 4.5 K. Among all the compounds, only 3 shows the ac-signals (ac, alternating current) and slow-relaxation behavior, which is a peculiar characteristic of a single-molecule magnet (SMM), giving a value of Ueff = 19.5(4) K. The present work thus contributes to the design of topologically unique discrete crystalline materials with notable functional properties. © 2020 American Chemical Society.

Authors
Akhtar M.N.1 , Aldamen M.A.2 , Khan J.3 , Shahid M.4 , Kirillov A.M. 5, 6
Publisher
American Chemical Society
Number of issue
10
Language
English
Pages
6545-6554
Status
Published
Volume
20
Year
2020
Organizations
  • 1 Department of Chemistry, Baghdad-ul-Jadeed Campus, Islamia University of Bahawalpur, Bahawalpur, 63100, Pakistan
  • 2 Department of Chemistry, School of Science, University of Jordan, Amman, 11942, Jordan
  • 3 School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China
  • 4 Functional Inorganic Materials Lab. (FIML), Department of Chemistry, Aligarh Muslim University, Aligarh, 202002, India
  • 5 Centro de Quĺmica Estrutural, Departamento de Engenharia Quĺmica, 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
Keywords
Coordination reactions; Crystallites; Magnetocaloric effects; Metallic compounds; Microcrystals; Nanocrystalline materials; Self assembly; Single crystals; Coordination clusters; Functional properties; Magnetocaloric effect (MCE); Microcrystalline solids; N-methyldiethanolamine; Self-assembly synthesis; Single-crystal X-ray diffraction studies; Single-molecule magnet; Topology
Date of creation
20.04.2021
Date of change
20.04.2021
Short link
https://repository.rudn.ru/en/records/article/record/72604/
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