Experimental and Theoretical Interpretation of the Magnetic Behavior of Two Dy(iii) Single-ion Magnets Constructed Through β-diketonate Ligands with Different Substituent Groups (-Cl/-OCH)

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 May 13

PMID 35557993

Authors

Sheng Zhang

Wenjiao Mo

Jiangwei Zhang

Haipeng Wu

Min Li

Xingqiang Lu

Bing Yin

Desuo Yang

Affiliations

Soon will be listed here.

Abstract

Two Dy(iii) single-ion magnets, formulated as [Dy(Phen)(Cl-tcpb)] (Cl-1) and [Dy(Phen)(CHO-tmpd)] (CHO-2) were obtained through β-diketonate ligands (Cl-tcpb = 1-(4-chlorophenyl)-4,4,4-trifluoro-1,3-butanedione and CHO-tmpd = 4,4,4-trifluoro-1-(4-methoxyphenyl)-1,3-butanedione) with different substituent groups (-Cl/-OCH) and auxiliary ligand, 1,10-phenanthroline (Phen). The Dy(iii) ions in Cl-1 and CHO-2 are eight-coordinate, with an approximately square antiprismatic (SAP, ) and trigonal dodecahedron ( ) NO coordination environment, respectively, in the first coordination sphere. Under zero direct-current (dc) field, magnetic investigations demonstrate that both Cl-1 and CHO-2 display dynamic magnetic relaxation of single-molecule magnet (SMM) behavior with different effective barriers ( ) of 105.4 cm (151.1 K) for Cl-1 and 132.5 cm (190.7 K) for CHO-2, respectively. As noted, compound CHO-2 possesses a higher effective barrier than Cl-1. From calculations, the energies of the first excited state (KD) are indeed close to the experimental as 126.7 cm 105.4 cm for Cl-1 and 152.8 cm 132.5 cm for CHO-2. The order of the calculated energies of KD is same as that of the experimental . The superior SIM properties of CHO-2 could have originated from the larger axial electrostatic potential (ESP) felt by the central Dy(iii) ion when compared with Cl-1. The larger ESP of CHO-2 arises from synergic effects of the more negative charge and shorter Dy-O distances of the axial O atoms of the first sphere. These charges and distances could be influenced by functional groups outside the first sphere, , -Cl and -OCH.

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