3d–4f magnetic exchange interactions and anisotropy in a series of heterobimetallic vanadium(iv)–lanthanide(iii) Schiff base complexes. Issue 39 (15th September 2021)

• Record Type: Journal Article
• Authors: Kotrle, Kamil; Nemec, Ivan; Moncol, Jan; Čižmár, Erik; Herchel, Radovan
• Is Part Of: Dalton transactions. Volume 50:Issue 39(2021)
• Page Start: 13883
• Page End: 13893
• Publication Date: 2021-09-15
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt01944a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : 3d–4f complexes were prepared and their X-ray analyses revealed changes in the coordination number upon changing the lanthanide (Gd → Er). The V IV –Ln III magnetic exchange was fit from magnetic data and calculated by DFT and CASSCF theoretical models. Abstract : A series of heterobimetallic Ln III –V IV compounds [Ln(VO)L(NO3 )3 (H2 O)] (Ln = Gd(1 ), Tb(2 ), Dy(3 ), and Er(4 )) assembled by a Schiff base ligand (H2 L = N, N ′-bis(1-hydroxy-2-benzylidene-6-methoxy)-1, 7-diamino-4-azaheptane) were prepared and studied with experimental and theoretical methods. The single-crystal X-ray analysis revealed the change of the coordination number from 10 found in 1–3 to 9 confirmed in 4 . The DC magnetic data were fit with several Hamiltonians to extract the exchange and anisotropy parameters of complexes 1–4 . This investigation of magnetic properties was carried out using both DFT and CASSCF theoretical calculations. It was found out that exchange interactions in 1, 3 and 4 are antiferromagnetic, while 2 has ferromagnetic exchange interactions. Moreover, the AC susceptibility measurements revealed the field-induced slow relaxation of magnetization in complexes 2 and 3 which is complicated by the presence of three relaxation channels. Nevertheless, these compounds belong to the first Tb III –V IV and Dy III –V IV single-molecule magnets in this class of compounds.