English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Zendy Open

Presents the pdf analysis as premium feature

PDF Analysis

Insights

Presents the summarisation as premium feature

Summarisation

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the zaia usage as premium feature

ZAIA

Zendy Tools

Zendy Plus

Presents the access of premium content as premium feature

Premium Content

Three  Pt 4 L 2 L′ 2   heteroleptic rectangles ( 1 – 3 ), containing ditopic redox‐active bis‐pyridine functionalized perylene bisimide (PBI) ligands  PBI‐pyr 2   ( L ) are reported. Co‐ligand  L′  is a dicarboxylate spacer of varying length, leading to modified overall size of the assemblies.  1 H NMR spectroscopy reveals a trend in the splitting and upfield chemical shift of the PBI‐hydrogens in the rectangles with respect to free PBI, most pronounced with the largest strut length ( 3 ) and least with the smallest strut length ( 1 ). This is attributed to increased rotational freedom of the  PBI‐pyr  2  ligand over its longitudinal axis (N py ‐N py ), due to increased distance between the PBI‐surfaces, which is corroborated by VT‐NMR measurements and DFT calculations. The intramolecular motion entails desymmetrization of the two PBI‐ligands, in line with cyclic voltammetry (CV) data. The first (overall two‐electron) reduction event and re‐oxidation for  1  display a subtle peak‐to‐peak splitting of 60 mV, whilst increased splitting of this event is observed for  2  and  3 . The binding of pyrene in  1  is probed to establish proof of concept of host‐guest chemistry enabled by the two PBI‐motifs. Fitting the binding curve obtained by  1 H NMR titration with a 1:1 complex formation model led to a binding constant of 964±55  m  −1 . Pyrene binding is shown to directly influence the redox‐chemistry of  1 , resulting in a cathodic and anodic shift of approximately 46 mV on the first and second reduction event, respectively.

Redox‐Active Supramolecular Heteroleptic M 4 L 2 L′ 2 Assemblies with Tunable Interior Binding Site