Work

Steric Hindrance and Secondary Interactions Govern Reconfiguration Between Two Complex Cu I Coordination Cages

Year: 2026

Type: article

Abstract: ABSTRACT A tetramine subcomponent featuring 1,5‐naphthylene arms was designed to exhibit extensive secondary interactions when assembled around stereochemically flexible tetracoordinate Cu I ions. Using 6‐methyl‐2‐formylpyridine, a [Cu I 12 L 6 ] 12+ pseudo‐hexagonal prismatic cage formed, stabilized by 29–32 C─H···π interactions and 12 arene stacking interactions. Replacing the aldehyde component with 3‐methyl‐2‐formylpyridine introduced steric clashes that partially prevented these interactions, leading instead to the formation of a [Cu I 8 L 4 ] 8+ rectangular open prism. The system exhibited structural interconversion: adding 6‐methyl‐2‐formylpyridine to the [Cu I 8 L 4 ] 8+ cage transformed it into the [Cu I 12 L 6 ] 12+ structure through selective displacement of 8 out of 24 aldehyde residues per cage, matching the number of sterically‐hindered positions predicted from structural analysis. This work demonstrates rational control over cage architecture through fine‐tuning of steric factors and intermolecular interactions, providing design principles for generating diverse structures from identical building blocks.

Source: Angewandte Chemie

DOI: 10.1002/ange.4287066

Authors: Houyang Xu, Sudhakar Gaikwad, Tanya K. Ronson, Jonathan R. Nitschke

Institution: University of Cambridge

Language: English

Topic: Supramolecular Chemistry and Complexes

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,790

Funders: Diamond Light Source, Engineering and Physical Sciences Research Council, European Research Council