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|a (KEY)0074867620150000054001809127newstructuraltypesofmn16singlemoleculemagnetswshap
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|a Thuijs, Annaliese E
|e verfasserin
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|a New structural types of Mn16 single-molecule magnets: W-shaped topology from reductive aggregation
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|c 2015
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|a Text
|b txt
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|a ohne Hilfsmittel zu benutzen
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|a Two new Mn16 clusters are reported: [Mn16O10(OH)3(OMe)8(O2CPhBut)17(MeOH)5] (2) and [Mn16O16(OMe)6(O2CPh)12(NO3)4(MeOH)2(H2O)4] (3). The complexes were obtained by reductive aggregation of MnO4– in CH2Cl2/MeOH, and oxidation of MnII and preformed (NnBu4)[Mn4IIIO2(O2CPh)9(H2O)] with CeIV, respectively. The core of 2 has a Mn16III core with an unusual 1:2:3:4:3:2:1 layer structure and a W-shaped pleated topology, whereas 3 contains a central 2 × 3 Mn6IV planar grid held within a nonplanar Mn10III loop and is a rare example of a complex with nitrate ions bridging like carboxylate ions. Variable-temperature, solid-state dc susceptibility, and ac susceptibility studies reveal that 2 and 3 possess S = 12 and S = 8 ground states, respectively. Fits of dc magnetization data collected over a temperature range of 1.8–4.0 K and a magnetization range of 0.1–4 T were fit to give S = 12, D = −0.16(2) cm–1, g = 1.98(3) for 2 and S = 8, D = −0.22(1) cm–1, g = 1.99(2) for 3, where D is the axial zero-field splitting parameter. The ac in-phase (χM′T) susceptibility below 15 K confirmed the ground-state spin values of 2 and 3, as determined from dc data, and the appearance of frequency-dependent out-of-phase (χM″) signals revealed that both complexes are new single-molecule magnets (SMMs). Fits of the ac data gave Ueff = 49.7(1) K and τ0 = 4.32 × 10–9 s for 2 and Ueff ≈ 14.0 ± 2 cm–1 and τ0 ≈ 3.2 ± 0.5 × 10–8 s for 3, where Ueff is the effective barrier to magnetization relaxation and τ0 is the pre-exponential factor. Thus, complexes 2 and 3 are two new members of a growing family of Mn16 clusters, and two new examples of high-nuclearity SMMs, with the Ueff for 2 approaching the value for the prototypical SMM family, [Mn12O12(O2CR)16(H2O)4].
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|a Chemical synthesis
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|a Magnetization
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|a Research
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|a Abboud, Khalil A
|4 oth
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|a King, Philippa
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|a Christou, George
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|i Enthalten in
|t Inorganic chemistry
|d Washington, DC [u.a.] : Soc., 1962
|g 54(2015), 18, Seite 9127
|w (DE-627)129095907
|w (DE-600)7558-9
|w (DE-576)014432145
|x 0020-1669
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|g volume:54
|g year:2015
|g number:18
|g pages:9127
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|u http://www.ncbi.nlm.nih.gov/pubmed/26352515
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