| Title: |
Assisted Self-Assembly to Target Heterometallic Mn-Nd and Mn-Sm SMMs: Synthesis and Magnetic Characterisation of [Mn$_{7}$Ln$_{3}$(O)$_{4}$(OH)$_{4}$(mdea)$_{3}$(piv)$_{9}$(NO$_{3}$)$_{3}$] (Ln=Nd, Sm, Eu, Gd)** |
| Authors: |
Kaemmerer, H.; Mereacre, V.; Ako, A. M.; Mameri, S.; Anson, C. E.; Clérac, R.; Powell, A. K. |
| Source: |
Chemistry - A European Journal, 27 (61), 15096-15102 ; ISSN: 0947-6539, 1521-3765 |
| Publisher Information: |
John Wiley and Sons |
| Publication Year: |
2021 |
| Collection: |
KITopen (Karlsruhe Institute of Technologie) |
| Subject Terms: |
ddc:600; Technology; info:eu-repo/classification/ddc/600 |
| Description: |
Assisted self-assembly by using a preformed [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] (1) (pivH=pivalic acid) cluster leads to 3 different outcomes of the reaction with Ln(NO$_{3}$)$_{3}$ ⋅ xH$_{2}$O (Ln=Pr−Ho and Y): Mn$_{7}$Ln$_{3}$ and in some cases the inverse butterfly Mn$_{2}$Ln$_{2}$ for Ln=Pr−Eu, Mn$_{5}$Ln$_{4}$ for Ln=Tb-Ho and in the special case of Gd all three possibilities can form. Whilst the magnetic properties for the Mn$_{5}$Ln$_{4}$ systems show the expected known SMM properties, for Mn$_{7}$Ln$_{3}$ two new examples of Nd- and Sm-containing SMMs have been discovered. in an assisted self-assembly approach starting from the [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] cluster a family of Mn−Ln compounds (Ln=Pr−Yb) was synthesised. The reaction of [Mn$_{6}$O$_{2}$(piv)$_{10}$(4-Me-py)$_{2}$(pivH)$_{2}$] (1) with N-methyldiethanolamine (mdeaH$_{2}$) and Ln(NO$_{3}$)$_{3}$ ⋅ 6H$_{2}$O in MeCN generally yields two main structure types: for Ln=Tb−Yb a previously reported Mn$_{5}$Ln$_{4}$ motif is obtained, whereas for Ln=Pr−Eu a series of Mn$_{7}$Ln$_{3}$ clusters is obtained. Within this series the Gd$^{III}$ analogue represents a special case because it shows both structural types as well as a third Mn$_{2}$Ln$_{2}$ 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 Mn$_{7}$Ln$_{3}$ analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=Nd$^{III}$(2), Sm$^{III}$(3) and Gd$^{III}$ (5) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K. |
| Document Type: |
article in journal/newspaper |
| File Description: |
application/pdf |
| Language: |
English |
| ISSN: |
0947-6539; 1521-3765 |
| Relation: |
info:eu-repo/semantics/altIdentifier/wos/000706746100001; info:eu-repo/semantics/altIdentifier/issn/0947-6539; info:eu-repo/semantics/altIdentifier/issn/1521-3765; https://publikationen.bibliothek.kit.edu/1000139383; https://publikationen.bibliothek.kit.edu/1000139383/130944400; https://doi.org/10.5445/IR/1000139383 |
| DOI: |
10.5445/IR/1000139383 |
| Availability: |
https://publikationen.bibliothek.kit.edu/1000139383; https://publikationen.bibliothek.kit.edu/1000139383/130944400; https://doi.org/10.5445/IR/1000139383 |
| Rights: |
https://creativecommons.org/licenses/by-nc-nd/4.0/deed.de ; info:eu-repo/semantics/openAccess |
| Accession Number: |
edsbas.2413FB35 |
| Database: |
BASE |