Low symmetry and functionalised organic cages prepared using Eglinton and Sonogashira coupling reactions

Figures & data

Scheme 1. Family of butadiyne cages reported by Sumby, Doonan and co-workers [31–33], and by us [37].

Scheme 2. Synthesis of tris-iodide half-cages 2, tris-alkyne half-cages 4, and hexanitrile-functionalised cages C^CN≡·≡C^CN and Si^CN≡·≡Si^CN.

Scheme 3. Synthesis of cages using Sonogashira reactions.

Scheme 4. Synthesis of tris-azide 5 and tris-triazole cage Si-trz-Si^H. The cage could not be fully purified, so an exact yield could not be calculated. However the yield of soluble unpurified material was 17%; based on¹H NMR spectroscopic analysis, we estimate the yield of cage formation is approximately 10%.

Figure 1. X-ray crystal structures of Si^CN≡·≡Si^CN, C^CN≡·≡C^CN crystallised from CHCl₃/pentane, and C^CN≡·≡C^CN crystallised from THF/toluene/methanol. In each case packing diagrams with a space-filling representation of the structures are shown. PLATON-SQUEEZE was used in the refinement of all structures [46].

Scheme 5. Post-synthetic modification of Si^CN≡·≡Si^CN to give hexa-cationic cage Si^amid≡·≡Si^amid·6Cl.

Thomas CM, Liang W, Preston D, et al. Post-synthetic modification of a porous hydrocarbon cage to give a Discrete Co 24 organometallic Complex. Chem: Eur J. 2022;28(51):e202200958. doi: 10.1002/chem.202200958

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