Working Paper
Authors
- Martina Cirulli ,
- Enrico Salvadori ,
- Zhi-Hui Zhang ,
- Michael Dommett ,
- Floriana Tuna ,
- Heiko Bamberger ,
- James Lewis ,
- Amanpreet Kaur ,
- Graham Tizzard ,
- Joris van Slageren ,
- Rachel Crespo Otero ,
- Stephen Goldup
UNIVERSITY OF SOUTHAMPTON ,
- Maxie Roessler
Abstract
Mechanically chelating
ligands have untapped potential for the engineering of metal ion properties by providing
reliable control of the number, nature and geometry of donor atoms, akin to how
a protein cavity controls the properties of bound metal ions. Here we
demonstrate this principle in the context of CoII-based single-ion
magnets. Using multi-frequency EPR, susceptibility and magnetization
measurements we found that these complexes show some of the highest zero field
splittings reported for five-coordinate CoII complexes to date. The
predictable coordination behavior of the interlocked ligands allowed the
magnetic properties of their CoII complexes to be evaluated
computationally a priori and our combined experimental and theoretical
approach enabled us to rationalize the observed trends. The predictable magnetic
behavior of the rotaxane CoII complexes demonstrates that interlocked
ligands offer a new strategy to design metal complexes with interesting
functionality.
Content

Supplementary material

2021 03 09 Cirulli SIM ESI
[Co(2)]2+(ClO4-)2
![Thumbnail image of [Co(2)]2+(ClO4-)2_checkcif.pdf](https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/60c75659567dfe17dbec647c/largeThumb/co-2-2-cl-o4-2-checkcif.jpg)
[Co(2)]2+(ClO4-)2 checkcif
[Co(3)]2+(ClO4-)2
![Thumbnail image of [Co(3)]2+(ClO4-)2_checkcif.pdf](https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/60c7565a337d6c847fe28df7/largeThumb/co-3-2-cl-o4-2-checkcif.jpg)
[Co(3)]2+(ClO4-)2 checkcif
Models de novo
Models from xray