Issue 24, 2020

From spin-crossover to single molecule magnetism: tuning magnetic properties of Co(ii) bis-ferrocenylterpy cations via supramolecular interactions with organocyanide radical anions

Abstract

TCNQ (7,7,8,8-tetracyanoquinodimethane) anion-radical derivatives were used to fine tune the magnetic properties of the [CoII(Fctp)2]2+ (Fctp = 4′-(2-ferrocenyl)-2,2′:6′2′′-terpyridine) cation in the solid state. The cocrystallization of [CoII(Fctp)2]2+ with TCNQ˙ yielded the two pseudo-polymorphic products [CoII(Fctp)2] (TCNQ)2 (1) and [CoII(Fctp)2] (TCNQ)2·MeCN (2) whereas the analogous reaction with TCNQF˙ (TCNQF = 2-fluoro-7,7,8,8-tetracyanoquinodimethane) exclusively yielded [CoII(Fctp)2] (TCNQF)2·MeCN (3). Compound 1 exhibits slow relaxation of magnetization under an applied DC field with Ueff = 19.1 K and τ0 = 9.8 × 10−6 s. Compounds 2 and 3 are isostructural but exhibit different spin-crossover behavior with transition temperatures of T1/2 = 336 K and 226 K, respectively. Investigations of the solid state structures by DFT calculations indicate that the differences in magnetic properties of the cationic moiety, [CoII(Fctp)2]2+, are induced by supramolecular interactions between [CoII(Fctp)2]2+ and tunable TCNQ˙/TCNQF˙ anion-radical derivatives.

Graphical abstract: From spin-crossover to single molecule magnetism: tuning magnetic properties of Co(ii) bis-ferrocenylterpy cations via supramolecular interactions with organocyanide radical anions

Supplementary files

Article information

Article type
Paper
Submitted
18 Feb 2020
Accepted
07 May 2020
First published
07 May 2020

J. Mater. Chem. C, 2020,8, 8135-8144

Author version available

From spin-crossover to single molecule magnetism: tuning magnetic properties of Co(II) bis-ferrocenylterpy cations via supramolecular interactions with organocyanide radical anions

H. Xie, K. R. Vignesh, X. Zhang and K. R. Dunbar, J. Mater. Chem. C, 2020, 8, 8135 DOI: 10.1039/D0TC00830C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements