Armenis Alexandros S, Vipanchi Vikram, Pantelis Konstantinos N, Cunha-Silva Luís, Vignesh Kuduva R, Alexandropoulos Dimitris I, Stamatatos Theocharis C
Department of Chemistry, University of Patras, 265 04, Patras, Greece.
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali Sector-81, Knowledge city, S.A.S. Nagar, Mohali, 140306, Punjab, India.
Chemistry. 2023 Nov 21;29(65):e202302337. doi: 10.1002/chem.202302337. Epub 2023 Oct 11.
The first use of the Schiff base chelate N-naphthalidene-o-aminophenol (naphH ) in Co/Ln chemistry has afforded a family of isostructural [Co Ln (OMe) (naph) (O CMe) (MeOH) ] (Ln=Tb, Dy and Er) complexes, revealing a rare {Co Ln(μ -OMe)} triangular core composed of two diamagnetic Co ions and a 4f-ion with slightly distorted square antiprismatic geometry. Alternating current (ac) magnetic susceptibility studies revealed that {Co Dy}, and its magnetic diluted analogue {Co Dy Y }, behave as mononuclear single-molecule magnets (SMMs) with similar energy barriers for the magnetization reversal, U , of ~85-90 K. SMM properties were also detected for {Co Er}, with the compound exhibiting a U of 18.7 K under an applied magnetic field of 800 Oe. To interpret the experimental magnetic results, ab initio CASSCF/RASSI-SO and DFT calculations were performed as a means of exploring the single-ion characteristics of Ln ions and comprehend the role of the diamagnetic Co ions in the magnetization relaxation of the three heterometallic compounds.
席夫碱螯合物N-萘叉邻氨基酚（naphH ）在钴/镧系化学中的首次应用得到了一系列同构的[Co Ln (OMe) (naph) (O CMe) (MeOH) ]（Ln = Tb、Dy和Er）配合物，揭示了一种罕见的由两个抗磁性钴离子和一个具有轻微扭曲的四方反棱柱几何构型的4f离子组成的{Co Ln(μ -OMe)}三角形核心。交流（ac）磁化率研究表明，{Co Dy}及其磁稀释类似物{Co Dy Y }表现为单核单分子磁体（SMMs），其磁化反转的能垒U 约为85 - 90 K。{Co Er}也检测到了SMM性质，该化合物在800 Oe的外加磁场下表现出18.7 K的U 。为了解释实验磁学结果，进行了从头算CASSCF/RASSI-SO和DFT计算，以探索镧系离子的单离子特性，并理解抗磁性钴离子在三种异金属化合物磁化弛豫中的作用。
