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Published on: June 23, 2023
Hexadecanuclear MnII2MnIII14 Molecular Torus Built from in Situ Tandem Ligand Transformations
Muhammad Riaz1, Rakesh Kumar Gupta1, Hai-Feng Su2
1Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials , Shandong University , Jinan , 250100 , People's Republic of China.
Abstract:
A mixed-valent hexadecanuclear manganese cluster, [MnII2MnIII14(trz)14(thetach)4(μ3-O)8(H2O)10](ClO4)6 (Mn16), containing two MnII and 14 MnIII ions, is constructed from mixed in situ generated ligands, 1,2,3-triazole (Htrz) and 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane (H3thetach). Remarkably, both ligands were not initially added into the reaction system, and their formations involve the in situ ligand decomposition and subsequent condensation reactions. The core of Mn16 is an elongated torus comprised of eight Mn atoms and four [Mn2O2] subunits bridged by oxo or alkoxide. The high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) of Mn16 dissolved in CH3CN indicates its structure remains intact as +3 and +4 species. Temperature and field dependent magnetization revealed predominantly antiferromagnetic exchange interactions within the cluster. The work provides one-pot synthesis of high-nuclearity manganese clusters using the ligands generated by in situ reactions in a tandem fashion.
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