Tetramine aspect ratio and flexibility determine framework symmetry for Zn8L6 self-assembled structures

DOI: 10.1002/anie.202217987

Authors: Jack A. Davies (University of Cambridge) , Andrew Tarzia (Imperial College London) , Tanya K. Ronson (University of Cambridge) , Florian Auras (Max-Planck-Institute of Microstructure Physics) , Kim E. Jelfs (Imperial College London) , Jonathan Russell Nitschke (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: January 2023
Diamond Proposal Number(s): 21497

Abstract: We derive design principles for the assembly of rectangular tetramines into Zn8L6 pseudo-cubic coordination cages. Because of the rectangular, as opposed to square, geometry of the ligand panels, and the possibility of either Δ or Λ handedness of each metal center at the eight corners of the pseudo-cube, many different cage diastereomers are possible. Each of the six tetra-aniline subcomponents investigated in this work assembled with zinc(II) and 2-formylpyridine in acetonitrile into a single Zn8L6 pseudo-cube diastereomer, however. Each product corresponded to one of four diastereomeric configurations, with T, Th, S6 or D3 symmetry. The preferred diastereomer for a given tetra-aniline subcomponent was shown to be dependent on its aspect ratio and conformational flexibility. Analysis of computationally modeled individual faces or whole pseudo-cubes provided insight as to why the observed diastereomers were favored.

Journal Keywords: Supramolecular Chemistry; Metal-Organic Cages; Stereochemistry; Self-Assembly

Subject Areas: Chemistry, Materials


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 16/01/2023 09:46

Discipline Tags:

Chemistry Materials Science Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)