Two- and Three-Spin Hybrid Inorganic-Organic [2]Rotaxanes Containing Metallated Salen Groups.

Autor: Bennett TS; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., Lockyer SJ; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., Asthana D; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., Whitehead GFS; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., Vitorica-Yrezabal IJ; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., Timco GA; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., Winpenny REP; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom., McInnes EJL; Department of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom.
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2024 Oct 16; Vol. 19 (20), pp. e202400641. Date of Electronic Publication: 2024 Sep 24.
DOI: 10.1002/asia.202400641
Abstrakt: Mono- and bis-salen functionalised [2]rotaxanes have been synthesised from the esterification of [2]rotaxanes containing phenol-terminated threads (salen=N,N'-bis(salicylidene)ethylenediamine). The [2]rotaxanes have general formula [RH][Cr 7 NiF 8 (O 2 C t Bu) 16 ], where [RH] + is a thread with a central secondary ammonium site that templates a [Cr 7 NiF 8 (O 2 C t Bu) 16 ] - ring. The threads are terminated at one or both ends by carboxylic acid functionalised salen groups. The {M(salen)} groups can be free-base [M=(H + ) 2 ] or metallated [M=Cu 2+ , Ni 2+ , (VO) 2+ ]. The [2]rotaxanes have been characterised by single crystal XRD and solid- and solution-state EPR spectroscopy. Where two paramagnetic M ions are involved [M=Cu 2+ and/or (VO) 2+ ] the [2]rotaxanes contain three electron spin S= 1 / 2 ${{ 1/2 }}$ centres, since the {Cr 7 Ni} ring has an S= 1 / 2 ${{ 1/2 }}$ ground state which is well isolated at low temperatures. These three-spin [2]rotaxanes have been characterised in solution by pulsed dipolar EPR spectroscopies (DEER, also known as PELDOR, and RIDME). The M⋅⋅⋅M and M⋅⋅⋅{Cr 7 Ni} interactions measured are consistent with dipolar interactions and also with the distances from single crystal XRD. The authors declare no competing financial interest.
(© 2024 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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