Ligand Design for Heterobimetallic Single‐Chain Magnets: Synthesis, Crystal Structures, and Magnetic Properties of M II Cu II (M=Mn, Co) Chains with Sterically Hindered Methyl‐Substituted Phenyloxamate Bridging Ligands

Two new series of neutral oxamato‐bridged heterobimetallic chains of general formula [MCu(L x ) 2 ]⋅ m  DMSO ( m =0–4) (L 1 = N ‐2‐methylphenyloxamate, M=Mn ( 1 a ) and Co ( 1 b ); L 2 = N ‐2,6‐dimethylphenyloxamate, M=Mn ( 2 a ) and Co ( 2 b ); L 3 = N ‐2,4,6‐trimethylphenyloxamate, M=Mn ( 3 a ) and Co ( 3 b )) have been prepared by reaction between the corresponding anionic oxamatocopper(II) complexes [Cu(L x ) 2 ] 2− with Mn 2+ or Co 2+ cations in DMSO. The crystal structures of [CoCu(L 2 ) 2 (H 2 O) 2 ] ( 2 b′ ) and [CoCu(L 3 ) 2 (H 2 O) 2 ]⋅4 H 2 O ( 3 b′ ) have been solved by single‐crystal X‐ray diffraction methods. Compounds 2 b′ and 3 b′ adopt zigzag and linear chain structures, respectively. The intrachain Cu⋅⋅⋅Co distance through the oxamate bridge is 5.296(1) Å in 2 b′ and 5.301(2) Å in 3 b′ , while the shortest interchain Co⋅⋅⋅Co distance is 5.995(5) Å in 2 b′ and 8.702(3) Å in 3 b′ , that is, the chains are well isolated in the crystal lattice due to the presence of the bulky methyl‐substituted phenyl groups. Although both Mn II Cu II and Co II Cu II chains exhibit ferrimagnetic behaviour with moderately strong intrachain antiferromagnetic coupling (− J Mn,Cu =24.7–27.9 cm −1 and − J Co,Cu =35.0–45.8 cm −1 ; H = ${{{}\mathrel{\mathop{\sum{}}\limits_{i}}{}}}$ − J M,Cu S M, i S Cu, i ), only the Co II Cu II chains show slow magnetic relaxation at low temperatures ( T B <3.5 K), which is characteristic of single‐chain magnets (SCMs) because of the high magnetic anisotropy of the Co II ion. The blocking temperatures T B along this series of chains vary according to the steric hindrance of the aromatic substituent of the oxamate ligand in the series L 1

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