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

Richard Winpenny, Tom s. Bennett, Selena j. Lockyer, Deepak Asthana, George f.s. Whitehead, Inigo j. Vitorica-Yrezabal, Grigore a. Timco, Eric j. l. Mcinnes

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Abstract

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][Cr7NiF8(O2CtBu)16], where [RH]+ is a thread with a central secondary ammonium site that templates a [Cr7NiF8(O2CtBu)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 = Cu2+, Ni2+, (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 = Cu2+ and/or (VO)2+] the [2]rotaxanes contain three electron spin S = ½ centres, since the {Cr7Ni} ring has an S = ½ 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···{Cr7Ni} interactions measured are consistent with dipolar interactions and also with the distances from single crystal XRD.

Original languageEnglish
Article numbere202400641
JournalChemistry: An Asian Journal
Early online date19 Jun 2024
DOIs
Publication statusE-pub ahead of print - 19 Jun 2024

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