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Syntheses, Crystal Structures, and Magnetic Properties of a Family of Tetra‐ and Octanuclear Mixed‐Valent Manganese Clusters
Author(s) -
Yang PeiPei,
Shao CongYing,
Zhu LiLi,
Xu Yun
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300582
Subject(s) - chemistry , manganese , perchlorate , ligand (biochemistry) , crystallography , crystal structure , magnetic susceptibility , stereochemistry , ion , organic chemistry , biochemistry , receptor
Reactions of manganese perchlorate and a quinquedentate Schiff base ligand (H 3 L ), derived from o ‐vanillin and 3‐amino‐1,2‐propanediol, together with a solution of coligands NaN 3 or NaO 2 CH or NaO 2 CPh in methanol produced three new tetranuclear manganese clusters that contain a mixed‐valent tetrahedral Mn II Mn III 3 core with the corresponding general formula [NaMn II Mn 3 III (μ 4 ‐O 2– )(H L ) 3 (N 3 ) 3 ]ClO 4 · 1.5H 2 O ( 1 ), [NaMn II Mn 3 III (μ 4 ‐O 2– )(H L ) 3 (HCO 2 ) 3 ]ClO 4 · 4H 2 O ( 2 ), and [NaMn II Mn 3 III (μ 4 ‐O 2– )(H L ) 3 (PhCO 2 )(H 2 O) 2 ](ClO 4 ) 2 (PhCO 2 ) · PhCO 2 H · H 2 O · CH 3 OH ( 3 ). According to the feature of the tetrahedral Mn II Mn III 3 core, we used a terephthalic acid disodium salt (Na 2 TA) instead of NaO 2 CPh and obtained an octanuclear manganese cluster that contained two tetrahedral Mn II Mn III 3 cores bridged by a TA 2– ligand with the general formula [Na 2 Mn 2 II Mn 6 III (μ 4 ‐O 2– ) 2 (H L ) 6 (HCO 2 ) 2 (CH 3 OH) 2 (TA)](TA)(ClO 4 ) 2 · 4CH 3 OH · 9.5H 2 O ( 4 ). Variable‐temperature, solid‐state direct‐current (dc) magnetization studies were carried out on compounds 1 – 4 in the 2.0–300 K range. The magnetic susceptibility data of these four compounds were fit to the theoretical χ m T versus T expression derived by the use of an isotropic Heisenberg spin Hamiltonian and the Van Vleck equation. The fitting results revealed the presence of both antiferromagnetic and ferromagnetic interactions between the metal centers.