期刊
DALTON TRANSACTIONS
卷 50, 期 13, 页码 4634-4642出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1dt00284h
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Three mononuclear manganese(iii) complexes based on flexible hexadentate ligands were synthesized, and the impact of ligand substituents was studied through various analyses. The complexes exhibit different spin-state switching behaviors, with complex 2 showing reversible two-step spin-state switching and complex 3 demonstrating incomplete spin-state switching. Single-crystal X-ray structural studies revealed the presence of three different spin states in complex 2 during the spin-state switching process. Electrochemical investigations showed that the reduced state of manganese(iii) centers in complex 3 is more easily accessible compared to complexes 1 and 2.
Three mononuclear manganese(iii) complexes based on flexible hexadentate ligands obtained from the condensation of N,N '-bis(3-aminopropyl)ethylenediamine and salicylaldehyde or salicylaldehyde with substitutions at the 5 or 3,5 positions, namely [Mn(X-sal(2)-323)](BPh4) (X = 5 H, 1; X = 5 Br, 2, and X = 3,5 Br, 3) have been synthesized. The impact of ligand substituents has been studied by variable temperature single-crystal X-ray diffraction analyses, and magnetic, spectroscopic and electrochemical investigations. The complexes have an analogous monocationic MnN4O2 surrounding offered by the flexible hexadentate ligand in a distorted octahedral geometry. Complex 1 remains in the high spin state over the entire temperature range, while complex 2 shows a reversible and complete two-step thermo-induced spin-state switching. An incomplete spin-state switching from a high spin to an intermediate high-spin low-spin (1 : 1) state was observed for complex 3. Single-crystal X-ray structural studies show the presence of three different spin states in 2 during the occurrence of the spin-state switching process. Electrochemical investigations showed that the reduced state of manganese(iii) centers in 3 is easily accessible in comparison to complexes 1 and 2.
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