Proton‐Induced Spin State Switching in an FeIII Complex

Author:

Kelly Conor T.1ORCID,Dunne Sean1,Kühne Irina A.1ORCID,Barker Andrew1,Esien Kane2,Felton Solveig2ORCID,Müller‐Bunz Helge1,Ortin Yannick1ORCID,Morgan Grace G.1ORCID

Affiliation:

1. School of Chemistry University College Dublin Belfield Dublin 4 Ireland

2. Centre for Nanostructured Media School of Mathematics and Physics Queen's University Belfast BT7 1NN Belfast UK

Abstract

AbstractReversible proton‐induced spin state switching of an FeIII complex in solution is observed at room temperature. A reversible magnetic response was detected in the complex, [FeIII(sal2323)]ClO4 (1), using Evans’ method 1H NMR spectroscopy which indicated cumulative switching from low‐spin to high‐spin upon addition of one and two equivalents of acid. Infrared spectroscopy suggests a coordination‐induced spin state switching (CISSS) effect, whereby protonation displaces the metal‐phenoxo donors. The analogous complex, [FeIII(4‐NEt2‐sal2323)]ClO4 (2), with a diethylamino group on the ligand, was used to combine the magnetic change with a colorimetric response. Comparison of the protonation responses of 1 and 2 reveals that the magnetic switching is caused by perturbation of the immediate coordination sphere of the complex. These complexes constitute a new class of analyte sensor which operate by magneto‐modulation, and in the case of 2, also yield a colorimetric response.

Funder

Science Foundation Ireland

Irish Research Council

European Cooperation in Science and Technology

University College Dublin

Publisher

Wiley

Subject

General Medicine

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