Tuning the Spin-Crossover Properties of FeII4L6 Cages via Ligand Modifications in the First and Second Coordination Spheres

11 October 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The effects of modifications to the first and second coordination spheres of the metal centers in FeII-based cages on the spin-crossover properties is not well understood. Here, we report a family of FeII4L6 spin-crossover cages based on 2,2’-pyridylbenzimidazoles where subtle modifications to the coordination motif (first coordination sphere) and the linker type (second coordination sphere) of the organic ligand lowered the spin crossover temperature in CD3CN to a range between 430 K and 244 K. Comparing pairs of cages, CH3 substituents on either the coordination motif or phenylene linker lowered the spin-crossover temperature by 48 K, 91 K or 186 K, attributed to predominantly first, second coordination sphere effects and a combination of both, respectively. This study provides first insight into how ligand modifications in the first and second coordination sphere can be harnessed on the path towards the improved rational design of spin-crossover cages.

Keywords

cage
self-assembly
spin-crossover
supramolecular chemistry

Supplementary materials

Title
Description
Actions
Title
Supporting Information
Description
Synthesis and characterisation details
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.