Compressed and expanded lattices - barriers to spin-state switching in Mn.sup.3+./sup. complexes

0573860 - FZÚ 2024 RIV US eng J - Journal Article
Harris, M.M. - Kühne, Irina A. - Kelly, C.T. - Jakobsen, V.B. - Jordan, R. - O’Brien, L. - Müller-Bunz, H. - Felton, S. - Morgan, G.G.
Compressed and expanded lattices - barriers to spin-state switching in Mn³⁺ complexes.
Crystal Growth & Design. Roč. 23, č. 6 (2023), s. 3996-4012. ISSN 1528-7483. E-ISSN 1528-7505
Institutional support: RVO:68378271
Keywords : spin crossover * manganese * coordination complex
OECD category: Inorganic and nuclear chemistry
Impact factor: 3.8, year: 2022
Method of publishing: Open access

We report the structural and magnetic properties of two new Mn3+ complex cations in the spin crossover [Mn(R-sal2323)]+ series, in lattices with seven different counterions in each case. We investigate the effect on the Mn3+ spin state of appending electron-withdrawing and electron-donating groups on the phenolate donors of the ligand. This was achieved by substitution of the ortho and para positions on the phenolate donors with nitro and methoxy substituents in both possible geometric isomeric forms. Using this design paradigm, the [MnL1]+ (a) and [MnL2]+ (b) complex cations were prepared by complexation of Mn3+ to the hexadentate Schiff base ligands with 3-nitro-5-methoxy-phenolate or 3-methoxy-5-nitro-phenolate substituents, respectively. A clear trend emerges with adoption of the spin triplet form in complexes 1a–7a, with the 3-nitro-5-methoxy-phenolate donors, and spin triplet, spin quintet and thermal SCO in complexes 1b–7b with the 3-methoxy-5-nitro-phenolate ligand isomer.
Permanent Link: https://hdl.handle.net/11104/0344212