Solid-state lattice effects on high-spin Mn(III) complexes with hexadentate Schiff-base ligand. Issue 7 (3rd July 2021)

• Record Type: Journal Article
• Authors: Wang, Yu-Ting; Xu, Peng-Yu; Yu, Zong-Mei; Wang, Zi-Kun; Wu, Hua-Yu; Wang, Shi; Li, Yong-Hua
• Is Part Of: Supramolecular chemistry. Volume 33:Issue 7(2021)
• Page Start: 380
• Page End: 389
• Publication Date: 2021-07-03
• Subjects: High spin -- hydrogen bonding -- crystal stacking -- manganese(III); Macromolecules -- Periodicals; Supramolecular chemistry -- Periodicals; 547.005
• DOI: 10.1080/10610278.2021.2025240
• Languages: English
• ISSNs: 1061-0278

Abstract

ABSTRACT: This paper reports the syntheses, crystal structures, magnetics and spectroscopic properties of high-spin (HS) salts of formula [Mn(salk-N-1, 5, 8, 12)]Y·S (Y = AsF6 for 1, Y = BF4, S = CH3 OH for 2, Y = PF6, S = CH3 OH for 3 ), where (salk-N-1, 5, 8, 12) 2− (2, 2ʹ-((2E, 14E)-3, 7, 10, 14-tetraazahexadeca-2, 14-diene-2, 15-diyl)diphenolate) is a hexadentate Schiff-base ligand. Crystal structural analysis indicates that the extensive hydrogen bonds play a primary role in stabilisation of their HS states. As an aid to understanding this behaviour, the crystal structure of the known spin crossover compound [Mn(sal-N-1, 5, 8, 12)]AsF6 (4 ) has been re-examined. To understand the impact of intermolecular forces to the different magnetic behaviours of salts 1 and 4, we evaluate of their supramolecular structures and confirm that intermolecular interactions can significantly affect the cooperativity. Furthermore, electrochemical studies on 1 and 4 shows that the choice of spin state is controlled by the solid-state lattice effects, i.e. cooperativity rather than molecular electronic effect. Graphical abstract: uf0001