Issue 17, 2021

The dynamic interplay between intramolecular and intermolecular interactions in mononuclear manganese(iii) SCO complexes

Abstract

The effect of counter anions on thermally induced manganese(III)-based SCO within the [Mn(5-F-sal-N-1,5,8,12)]Y family has been investigated. All the complexes are crystallized without any lattice solvents. Crystal packing and intermolecular forces influence the spin-state stabilization and spin-transition profiles. Magnetic measurements indicate that salts with octahedral anions, [Mn(5-F-sal-N-1,5,8,12)]PF6 (1), [Mn(5-F-sal-N-1,5,8,12)]AsF6 (2) and [Mn(5-F-sal-N-1,5,8,12)]SbF6 (3), show HS electronic configurations between 2 and 300 K, and there exist π–π stackings between the phenyl groups from the neighboring [Mn(5-F-sal-N-1,5,8,12)]+ cations. As for the tetrahedral anions, complex [Mn(5-F-sal-N-1,5,8,12)]BF4 (4) exhibits a gradual and incomplete spin conversion. Complex [Mn(5-F-sal-N-1,5,8,12)] ClO4 (5) shows a nearly complete SCO with T1/2 = 100 K. The remaining salts with spherical anions form Nam–H⋯X (X = Cl, Br, I) hydrogen bonds between Mn(III) cations and counterions. Complexes [Mn(5-F-sal-N-1,5,8,12)]Cl (6) and [Mn(5-F-sal-N-1,5,8,12)] Cl0.28Br0.72 (7) feature gradual SCO behaviors with T1/2 = 220 K and 235 K, respectively. Complex [Mn(5-F-sal-N-1,5,8,12)]I (8) exhibits a more gradual spin conversion and is far from a complete HS state with a χMT value of 1.89 cm3 mol−1 K at 400 K.

Graphical abstract: The dynamic interplay between intramolecular and intermolecular interactions in mononuclear manganese(iii) SCO complexes

Supplementary files

Article information

Article type
Paper
Submitted
02 Dec 2020
Accepted
25 Mar 2021
First published
26 Mar 2021

Dalton Trans., 2021,50, 5899-5910

The dynamic interplay between intramolecular and intermolecular interactions in mononuclear manganese(III) SCO complexes

C. Qin, S. Zhao, H. Wu, Y. Li, Z. Wang, Z. Wang and S. Wang, Dalton Trans., 2021, 50, 5899 DOI: 10.1039/D0DT04109B

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