Single-Molecule Magnets: Novel Mn8 and Mn9 Carboxylate Clusters Containing an Unusual Pentadentate Ligand Derived from Pyridine-2,6-dimethanol
作者： Colette Boskovic , Wolfgang Wernsdorfer , Kirsten Folting , John C. Huffman , David N. Hendrickson
DOI: 10.1021/IC020217P
关键词: Chemistry 、 Deprotonation 、 Pyridine 、 Magnetization 、 Magnetic susceptibility 、 Crystal structure 、 Crystallography 、 Carboxylate 、 Stereochemistry 、 Ligand 、 Triclinic crystal system
摘要: The reactions of the Mn(III)(3) and Mn(II)Mn(III)(2) complexes [Mn(3)O(O(2)CEt)(6)(py)(3)][ClO(4)] [Mn(3)O(O(2)CEt)(6)(py)(3)] with pyridine-2,6-dimethanol (pdmH(2)) afford mixed-valence Mn(II)(6)Mn(III)(2) octanuclear complex [Mn(8)O(2)(py)(4)(O(2)CEt)(8)(L)(2)][ClO(4)](2) (1) Mn(II)(7)Mn(III)(2) enneanuclear [Mn(9)(O(2)CEt)(12)(pdm)(pdmH)(2)(L)(2)] (2), respectively. Both compounds contain a novel pentadentate ligand, dianion (6-hydroxymethylpyridin-2-yl)-(6-hydroxymethylpyridin-2-ylmethoxy)methanol (LH(2)), which is hemiacetal formed in situ from Mn-assisted oxidation pdmH(2). Complex 1 crystallizes monoclinic space group P2(1)/n following cell parameters at -160 degrees C: = 16.6942(5) A, b 13.8473(4) c 20.0766(6) beta 99.880(1) degrees, V 4572.27 A(3), Z 2, R (R(w)) 4.78 (5.25). 2.0.2MeCN triclinic Ponemacr; -157 12.1312(4) 18.8481(6) 23.2600(7) alpha 78.6887(8) 77.9596(8) gamma 82.3176(8) 5076.45 4.12 (4.03). are new structural types comprising distorted-cubane units linked together, albeit two very different ways. In addition, 2 features three distinct binding modes for chelating ligands derived deprotonated Complexes were characterized by variable-temperature ac dc magnetic susceptibility measurements found to possess spin ground states 0 11/2, Least-squares fitting reduced magnetization data gave S g 2.0, D -0.11 cm(-1) where axial zero-field splitting parameter. Direct current versus field studies on <1 K show hysteresis behavior <0.3 K, establishing as single-molecule magnet. Magnetization decay an effective barrier relaxation U(eff) 3.1 4.5 K.
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