Periphery-Functionalized Porous Organic Cages

Paul S Reiss; Marc A Little; Valentina Santolini; Samantha Y Chong; Tom Hasell; Kim E Jelfs; Michael E Briggs; Andrew I Cooper

doi:10.1002/chem.201603593

Periphery-Functionalized Porous Organic Cages

Chemistry. 2016 Nov 7;22(46):16547-16553. doi: 10.1002/chem.201603593. Epub 2016 Oct 6.

Authors

Paul S Reiss¹, Marc A Little², Valentina Santolini³, Samantha Y Chong², Tom Hasell², Kim E Jelfs³, Michael E Briggs⁴, Andrew I Cooper⁵

Affiliations

¹ Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
² Department of Chemistry and Materials Innovation Factory, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
³ Department of Chemistry, Imperial College London, South Kensington, London, SW7 2AZ, UK.
⁴ Department of Chemistry and Materials Innovation Factory, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK. mebriggs@liverpool.ac.uk.
⁵ Department of Chemistry and Materials Innovation Factory, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK. aicooper@liverpool.ac.uk.

PMID: 27709721
DOI: 10.1002/chem.201603593

Abstract

By synthesizing derivatives of a trans-1,2-diaminocyclohexane precursor, three new functionalized porous organic cages were prepared with different chemical functionalities on the cage periphery. The introduction of twelve methyl groups (CC16) resulted in frustration of the cage packing mode, which more than doubled the surface area compared to the parent cage, CC3. The analogous installation of twelve hydroxyl groups provided an imine cage (CC17) that combines permanent porosity with the potential for post-synthetic modification of the cage exterior. Finally, the incorporation of bulky dihydroethanoanthracene groups was found to direct self-assembly towards the formation of a larger [8+12] cage, rather than the expected [4+6], cage molecule (CC18). However, CC18 was found to be non-porous, most likely due to cage collapse upon desolvation.

Keywords: cage compounds; cycloimination; gas sorption; microporous materials.