Assembling Hexagonal-Bipyramidal {Mn8Zn2} and {Mn8Zn4} Clusters

Thomais G. Tziotzi, Evangelos K. Andreou, Athanasios Mavromagoulos, Mark Murrie, Scott J. Dalgarno, Euan K. Brechin, Constantinos J. Milios

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Article numbere202200434
JournalEuropean Journal of Inorganic Chemistry
Volume2022
Issue number32
Early online date5 Sep 2022
DOIs
Publication statusPublished - 17 Nov 2022

Keywords

  • Heterometallic clusters
  • Magnetic properties
  • Manganese
  • Synthesis design
  • Zinc

ASJC Scopus subject areas

  • Inorganic Chemistry

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