Close Encounters of the Weak Kind: Investigations of Electron-Electron Interactions Between Dissimilar Spins in Hybrid Rotaxanes

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Aug 15

PMID 31411874

Citations 6

Authors

Selena J Lockyer

Alistair J Fielding

George F S Whitehead

Grigore A Timco

Richard E P Winpenny

Eric J L McInnes

Affiliations

Soon will be listed here.

Abstract

We report a family of hybrid [2]rotaxanes based on inorganic [CrNiF(OCBu)] ("{CrNi}") rings templated about organic threads that are terminated at one end with pyridyl groups. These rotaxanes can be coordinated to [Cu(hfac)] (where Hhfac = 1,1,1,5,5,5-hexafluoroacetylacetone), to give 1:1 or 1:2 Cu:{CrNi} adducts: {[Cu(hfac)](py-CHNHCHCHPh)[CrNiF(OCBu)]}, {[Cu(hfac)][py-CHNHCHCH][CrNiF(OCBu)]}, {[Cu(hfac)]([py-CHCHNHCHCHSCH][CrNiF(OCBu)])}, {[Cu(hfac)]([py-CH-CHNH(CH)Ph][CrNiF(OCBu)])}, and {[Cu(hfac)]([3-py-CHCHNH(CH)SCH][CrNiF(OCBu)])}, the structures of which have been determined by X-ray diffraction. The {CrNi} rings and Cu ions both have electronic spin = 1/2, but with very different -values. Continuous-wave EPR spectroscopy reveals the exchange interactions between these dissimilar spins, and hence the communication between the different molecular components that comprise these supramolecular systems. The interactions are weak such that we observe AX or AX type spectra. The connectivity between the {CrNi} ring and thread terminus is varied such that the magnitude of the exchange interaction can be tuned. The coupling is shown to be dominated by through-bond rather than through-space mechanisms.

Citing Articles

Characterizing X-Ray and Solution State Conformations for a Model Qubit System: {CrNi} Ring Rotaxanes on a Mixed Metal Triangle.

Loci L, Lockyer S, Bennett T, Rogers C, Brookfield A, Timco G Inorg Chem. 2024; 63(48):22880-22891.

PMID: 39550763 PMC: 11615942. DOI: 10.1021/acs.inorgchem.4c03919.

Control and Transferability of Magnetic Interactions in Supramolecular Structures: Trimers of {Cr Ni} Antiferromagnetic Rings.

Lockyer S, Asthana D, Whitehead G, Vitorica-Yrezabal I, Timco G, McInnes E Chemistry. 2023; 29(69):e202302360.

PMID: 37737455 PMC: 10947047. DOI: 10.1002/chem.202302360.

Modelling Conformational Flexibility in a Spectrally Addressable Molecular Multi-Qubit Model System.

Rogers C, Asthana D, Brookfield A, Chiesa A, Timco G, Collison D Angew Chem Int Ed Engl. 2022; 61(45):e202207947.

PMID: 36222278 PMC: 9828767. DOI: 10.1002/anie.202207947.

Five-Spin Supramolecule for Simulating Quantum Decoherence of Bell States.

Lockyer S, Chiesa A, Brookfield A, Timco G, Whitehead G, McInnes E J Am Chem Soc. 2022; 144(35):16086-16092.

PMID: 36007954 PMC: 9460766. DOI: 10.1021/jacs.2c06384.

Targeting molecular quantum memory with embedded error correction.

Lockyer S, Chiesa A, Timco G, McInnes E, Bennett T, Vitorica-Yrezebal I Chem Sci. 2021; 12(26):9104-9113.

PMID: 34276940 PMC: 8261727. DOI: 10.1039/d1sc01506k.

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