In:
Dalton Transactions, Royal Society of Chemistry (RSC), Vol. 50, No. 47 ( 2021), p. 17566-17572
Abstract:
The reaction of MnCl 2 ·4H 2 O, H 8 L (2,2′-bis- p - t Bu-calix[4]arene) and NEt 3 in a dmf/MeOH solvent mixture results in the formation of a mixed valent decametallic cluster of formula [MnII6MnIII4(L) 2 (μ 3 -OH) 4 (μ-OH) 4 (MeOH) 4 (dmf) 4 (MeCN) 2 ]·MeCN (3). Complex 3 crystallises in the monoclinic space group P 2 1 / n with the asymmetric unit comprising half of the compound. Structure solution reveals that the bis-calix[4]arene ligands are arranged such that one TBC[4] moiety in each has undergone inversion in order to accommodate a [MnIII4MnII6] metallic skeleton that describes three vertex-sharing [MnIII2MnII2] butterflies. The structure is closely related to the species [MnIII6MnII4(L) 2 (μ 3 -O) 2 (μ 3 -OH) 2 (μ-OMe) 4 (H 2 O) 4 (dmf) 8 ]·4dmf (4), the major difference being the oxidation level of the Mn ions in the core of the compound. DFT calculations on the full structures reveal that replacing the Mn III ions in 4 for Mn II ions in 3 results in a significant decrease in the magnitude of some antiferromagnetic exchange contributions, a switch from ferromagnetic to antiferromagnetic in others, and the loss of significant spin frustration.
Type of Medium:
Online Resource
ISSN:
1477-9226
,
1477-9234
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2021
detail.hit.zdb_id:
1472887-4
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