abstract
A novel dynamic [3]catenane consisting of a large four-station central macrocycle which incorporates a bay tetrachloro-functionalized perylene diimide (PDI) unit and two triazolium anion-binding motifs, mechanically bonded with two smaller isophthalamide-containing macrocycles, is constructed using an anion template synthetic methodology. Proton NMR, electronic absorption, and fluorescence emission spectroscopies together with molecular dynamics simulations are used to investigate the anion recognition- and solvent-dependent dynamic properties of the higher-order mechanically interlocked molecule. Importantly, unprecedented solvent-dependent and anion-binding induced circumrotatory motion in a hetero[3]catenane system is demonstrated where the exotic dual rotary switching behavior provides a unique and sophisticated mechanism for optical anion sensing in competitive protic organic and aqueous-organic media.
keywords
ARTIFICIAL MOLECULAR MACHINES; BISIMIDE DYES; SUPRAMOLECULAR CHEMISTRY; TRANSLATIONAL ISOMERISM; AROMATIC INTERACTIONS; COMPETITIVE-BINDING; BAY SUBSTITUENTS; PI INTERACTIONS; COMPLEXATION; RECOGNITION
subject category
Chemistry
authors
Barendt, TA; Ferreira, L; Marques, I; Felix, V; Beer, PD
our authors
Igor Oliveira Marques
Junior Researcher
Vítor Félix
Associate Professor with AggregationProjects
acknowledgements
The theoretical studies were supported by project P2020-PTDC/QEQ-SUP/4283/2014 as well as by CICECO-Aveiro Institute of Materials (UID/CTM/50011/2013) and iBiMED-Institute of Biomedicine (UID/BIM/04501/2013), financed by National Funds through the FCT/MEC and, when applicable, co-financed by FEDER through COMPETE, under the PT2020 Partnership Agreement. I.M. thanks the FCT for the Ph.D. scholarship SFRH/BD/87520/2012. T.A.B. would like to thank the EPSRC and Christ Church, University of Oxford, for funding.