title: Fine Tuning of the Anisotropy Barrier by Ligand Substitution Observed in Linear {Dy2Ni2} Clusters.
abstract: Three new heterometallic single-molecule magnets (SMMs), [Dy2Ni2(bipy)2(RC6H4COO)10] [bipy=2,2'-bipyridine, R=H (1), CH3(2), and NO2(3)], are synthesized solvothermally with different 3-substituted benzoate ligands (RC6H4COO-), and are characterized both structurally and magnetically. Structural analyses reveal that the three entities are structurally analogous, exhibiting an approximately linear {Dy2Ni2} core bridged by ten carboxylate moieties from the RC6H4COO-ligands. A noncoordinating substituent group attached on the phenyl ring results in minor geometry distortions of 1-3, but causes a significant decrease in the Mulliken atomic charge on the axially shortest O donor through inductive and/or conjugative effects. Weak intramolecular ferromagnetic (for DyIII⋅⋅⋅DyIII) and antiferromagnetic (for DyIII⋅⋅⋅NiII) interactions with slightly different coupling strengths are observed in 1-3 at low temperatures, and the effective anisotropy barriers to block the magnetization reversal are 39.9, 25.9, and 2.8 cm-1, respectively, under zero direct-current field. Ab initio calculations reveal that ligand substitution by the noncoordinating electron-withdrawing/electron-donating group can give rise to good modulation of the energy gap between the two lowest Kramers doublets, as well as the orientation of the local easy axis of the DyIIIion magnetization. The directions of the local easy axis of the DyIIIion can further influence the dipole spin-spin interaction and the molecular anisotropy of the entire molecule, which, together with the energy separation between the ground and first excited ground states, become the significant factors determining the effective anisotropy barrier heights of 1-3. These important results demonstrate that the charge distributions of the ligand-field environments play essential roles in SMM performance, which should be considered seriously and utilized efficiently during the rational design of new, more feasible and practical SMMs.
authors.affiliation: College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin, 300387, P.R. China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Li
authors.affiliation: College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin, 300387, P.R. China.
authors.forename: Qiu
authors.initials: Q
authors.lastname: Shang
authors.affiliation: Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing, 210023, P.R. China.
authors.forename: Yi-Quan
authors.initials: YQ
authors.lastname: Zhang
authors.affiliation: College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin, 300387, P.R. China.
authors.forename: En-Cui
authors.initials: EC
authors.lastname: Yang
authors.affiliation: College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin, 300387, P.R. China.|Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300071, P.R. China.
authors.forename: Xiao-Jun
authors.initials: XJ
authors.lastname: Zhao
keywords: anisotropy barriers; crystal structures; heterometallic complexes; ligand substitution; magnetic properties; single-molecule magnets