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- Title
Assembling Hexagonal‐Bipyramidal {Mn<sub>8</sub>Zn<sub>2</sub>} and {Mn<sub>8</sub>Zn<sub>4</sub>} Clusters.
- Authors
Tziotzi, Thomais G.; Andreou, Evangelos K.; Mavromagoulos, Athanasios; Murrie, Mark; Dalgarno, Scott J.; Brechin, Euan K.; Milios, Constantinos J.
- Abstract
Reaction between Mn(NO3)2 ⋅ 6H2O, Zn(NO3)2 ⋅ 6H2O, 1,3,5‐tri(2‐hydroxyethyl)‐1,3,5‐triazacyclohexane (H3L) and pyrazole in MeOH under basic conditions leads to the formation of the decanuclear complex [MnIII6MnII2ZnII2(L)2(pyr)4O4(OH)4(NO3)2 (MeOH)2(H2O)4](NO3)2 ⋅ Η2Ο (1 ⋅ Η2Ο). The metallic core of the cationic cluster consists of a central hexagonal‐bipyramidal {MnIII4MnII2ZnII2} unit connected to two peripheral trivalent Mn centers arranged in a "trans" fashion, with one MnIII center lying above and one MnIII center below the hexagonal plane. Replacing Mn(NO3)2 ⋅ 6H2O with MnBr2 ⋅ 4H2O and repeating the same reaction leads to the formation of the related, neutral decanuclear complex [MnIII6MnII2ZnII2(L)2(pyr)4O4(OH)4Br4(H2O)2] (2), displaying the same metallic core as 1. Addition of THF to the reaction mixture that produces (2) affords the neutral dodecanuclear complex [MnIII6MnII2ZnII4(L)2(pyr)6O4(OH)4Br6(H2O)4] ⋅ 8THF (3 ⋅ 8THF), whose metallic skeleton retains the central hexagonal‐bipyramidal {MnIII4MnII2ZnII2} unit found in 1 and 2 but is now connected to two peripheral {MnIIIZnII} units. Magnetic susceptibility and magnetization measurements carried out in the T=2–300 K temperature range and in fields up to B=7.0 T for all three complexes reveal dominant antiferromagnetic exchange interactions.
- Subjects
MAGNETIC susceptibility; MAGNETIZATION measurement; ADDITION reactions; PYRAZOLES; MAGNETIC properties
- Publication
European Journal of Inorganic Chemistry, 2022, Vol 2022, Issue 32, p1
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.202200434