In:
Angewandte Chemie, Wiley, Vol. 135, No. 29 ( 2023-07-17)
Abstract:
The engineering of intermolecular interaction is challenging but critical for magnetically switchable molecules. Here, we prepared two cyanide‐bridged [Fe 4 Co 4 ] cube complexes via the alkynyl‐ and alcohol‐functionalized trispyrazoyl capping ligands. The alkynyl‐functionalized complex 1 exhibited a thermally‐induced incomplete metal‐to‐metal electron transfer (MMET) behaviour at around 220 K, while the mixed alkynyl/alcohol‐functionalized cube of 2 showed a complete and abrupt MMET behaviour at 232 K. Remarkably, both compounds showed a long‐lived photo‐induced metastable state up to 200 K. The crystallographic study demonstrated that the incomplete transition of 1 was likely due to the possible elastic frustration originating from the competition between the anion‐propagated elastic interactions and inter‐cluster alkynyl‐alkynyl & CH‐alkynyl interactions, whereas the latter are eliminated in 2 as a result of the partial substitution by the alcohol‐functionalized ligand. Additionally, the introduction of chemically distinguishable cobalt centers within the cube unit of 2 did not lead to a two‐step but a one‐step transition, possibly because of the strong ferroelastic intramolecular interaction through the cyanide bridges.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.29
DOI:
10.1002/ange.202301124
Language:
English
Publisher:
Wiley
Publication Date:
2023
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