A family of manganese rods:: Syntheses, structures, and magnetic properties

被引:168
作者
Rajaraman, G
Murugesu, M
Sañudo, EC
Soler, M
Wernsdorfer, W
Helliwell, M
Muryn, C
Raftery, J
Teat, SJ
Christou, G
Brechin, EK
机构
[1] Univ Manchester, Dept Chem, Manchester M13 9PL, Lancs, England
[2] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[3] SERC, Daresbury Lab, CCLRC, Warrington WA4 4AD, Cheshire, England
[4] CNRS, Lab Louis Neel, F-38042 Grenoble 9, France
[5] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland
关键词
D O I
10.1021/ja0471929
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of the mixed-valent metal triangles [Mn3O(O2CR)(6)(py)(3)] (R = CH3, Ph, C(CH3)(3)) with the tripodal ligands H(3)thme (1,1,1-tris(hydroxymethyl)ethane) and H(3)tmp (1,1,1-tris(hydroxymethyl)propane) in MeCN, produces a family of manganese rodlike complexes whose structures are all derived from a series of edge-sharing triangles. Variable temperature direct current (dc) magnetic susceptibility data were collected for all complexes in the 1.8-300 K temperature range in fields up to 7.0 T. Complex 1, [Mn12O4(OH)(2)(PhCOO)(12)(thme)(4)(py)(2)], has an S = 7 ground state with the parameters g = 1.98 and D = -0.13 K. Complex 2, [Mn8O4((CH3)(3)CCO2)(10)(thme)(2)(py)(2)] has a ground state of S= 6, with g= 1.81 and D = -0.36 K. Complex 3, [Mn7O2(PhCO2)(9)(thme)(2)(py)(3)], has a spin ground states of S = 7 with the parameters g = 1.78 and D = -0.20 K. The best fit for complex 4, [Mn-6((CH3)(3)CCO2)(8)(tmp)(2)(py)(2)], gave a spin ground state of S = 3 with the parameters g = 1.73 and D = -0.75 K, but was of poorer quality than that normally obtained. The presence of multiple Mn2+ ions in the structure of 4 leads to the presence of low-lying excited states with energy levels very close to the ground state, and in the case of complex 5, [Mn-6(CH3CO2)(6)(thme)(2)(H(2)tea)(2)], no satisfactory fit of the data was obtained. DFT calculations on 4 and 5 indicate complexes with spin ground states of S = 4 and S = 0 respectively, despite their topological similarities. Single-crystal hysteresis loop and relaxation measurements show complex 1 to be a SMM.
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页码:15445 / 15457
页数:13
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