Issue 25, 2019

Anionic guest-dependent slow magnetic relaxation in Co(ii) tripodal iminopyridine complexes

Abstract

We report the syntheses and magnetic property characterizations of four mononuclear cobalt(II) complex salts featuring a tripodal iminopyridine ligand with external anion receptor groups, [CoL5-ONHtBu]X2 (X = Cl (1), Br (2), I (3) and ClO4 (4)). While all four salts exhibit anion binding through pendant amide moieties, only in the case of 1 is field-induced slow relaxation of magnetisation observed, whereas in the other salts this phenomenon is absent at the limits of our instrumentation. The effect of chloride inducing a seventh Co–N interaction and concomitant structural distortion is hypothesized as the origin of the observed dynamic magnetic properties observed in 1. Ab initio computational studies carried out on a 7-coordinate Co(II) model species survey the complex interplay of coordination number and trigonal twisting on the sign and magnitude of the axial anisotropy parameter (D), and identify structural features whose distortions can trigger large switches in the sign and magnitude of magnetic anisotropy.

Graphical abstract: Anionic guest-dependent slow magnetic relaxation in Co(ii) tripodal iminopyridine complexes

Supplementary files

Article information

Article type
Paper
Submitted
18 Febr. 2019
Accepted
24 Febr. 2019
First published
25 Febr. 2019

Dalton Trans., 2019,48, 9117-9126

Author version available

Anionic guest-dependent slow magnetic relaxation in Co(II) tripodal iminopyridine complexes

C. M. Klug, T. J. Ozumerzifon, I. Bhowmick, B. N. Livesay, A. K. Rappé and M. P. Shores, Dalton Trans., 2019, 48, 9117 DOI: 10.1039/C9DT00739C

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