Assisted Self-Assembly to Target Heterometallic Mn-Nd and Mn-Sm SMMs: Synthesis and Magnetic Characterisation of [Mn7Ln3(O)4(OH)4(mdea)3(piv)9(NO3)3] (Ln=Nd,Sm, Eu,Gd)** |
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| Authors: | Hagen Kaemmerer Dr Valeriu Mereacre Dr Ayuk M Ako Dr Samir Mameri Dr Christopher E Anson Dr Rodolphe Clérac Prof Annie K Powell |
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| Institution: | 1. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, 76131 Karlsruhe, Germany;2. Université de Strasbourg, IUT Robert Schuman, CS 10315, 67411 Illkirch Cedex, France;3. Univ. Bordeaux CNRS, Centre de Recherche Paul Pascal UMR 5031, 33600 Pessac, France |
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| Abstract: | In an assisted self-assembly approach starting from the Mn6O2(piv)10(4-Me-py)2(pivH)2] cluster a family of Mn?Ln compounds (Ln=Pr?Yb) was synthesised. The reaction of Mn6O2(piv)10(4-Me-py)2(pivH)2] ( 1 ) with N-methyldiethanolamine (mdeaH2) and Ln(NO3)3 ? 6H2O in MeCN generally yields two main structure types: for Ln=Tb?Yb a previously reported Mn5Ln4 motif is obtained, whereas for Ln=Pr?Eu a series of Mn7Ln3 clusters is obtained. Within this series the GdIII analogue represents a special case because it shows both structural types as well as a third Mn2Ln2 inverse butterfly motif. Variation in reaction conditions allows access to different structure types across the whole series. This prompts further studies into the reaction mechanism of this cluster assisted self-assembly approach. For the Mn7Ln3 analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=NdIII( 2 ), SmIII( 3 ) and GdIII ( 5 ) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K. |
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| Keywords: | manganese lanthanides assisted self-assembly single-molecule magnets cooperativity |
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