The “Magic Linker”: Highly Effective Gelation from Sterically Awkward Packing

Smith, James P.; Yufit, Dmitry S.; McCabe, James F.; Steed, Jonathan W.

doi:10.1021/acs.cgd.1c01470

The “Magic Linker”: Highly Effective Gelation from Sterically Awkward Packing

Smith, James P.; Yufit, Dmitry S.; McCabe, James F.; Steed, Jonathan W.

Authors

James P. Smith

Dr Dmitry Yufit d.s.yufit@durham.ac.uk
Academic Visitor

James F. McCabe

Professor Jonathan Steed jon.steed@durham.ac.uk
Professor

Abstract

Bis(urea)s based on the 4,4′-methylenebis(2,6-diethylphenylene) (4,4′-MDEP) spacer are highly effective low molecular weight gelators, and the first single crystal structure of a bis(urea) based on this spacer is reported. The structure is a conformational isomorph with eight crystallographically independent molecules (Z′ = 8) arranged in four tennis-ball type dimers with the 2,6-diethylphenylene units adopting five different conformations in the ratio 4:5:3:2:2. The awkward shape and conformational promiscuity arising from the orientations of the ethyl groups in this system is linked to its gelation behavior. A total of seven 4,4′-MDEP derivatives have been prepared, and six are versatile gelators, confirming the particularly effective nature of the MDEP spacer. Only the nitrophenyl derivative does not form gels, likely because of intramolecular CH···O hydrogen bonding arising from the electron-withdrawing nature of the nitro substituent and hence inhibition of the urea α-tape hydrogen-bonded motif.

Citation

Smith, J. P., Yufit, D. S., McCabe, J. F., & Steed, J. W. (2022). The “Magic Linker”: Highly Effective Gelation from Sterically Awkward Packing. Crystal Growth and Design, 22(3), 1914-1921. https://doi.org/10.1021/acs.cgd.1c01470

Journal Article Type	Article
Online Publication Date	Feb 9, 2022
Publication Date	Mar 2, 2022
Deposit Date	Apr 27, 2022
Publicly Available Date	Aug 17, 2022
Journal	Crystal Growth and Design
Print ISSN	1528-7483
Electronic ISSN	1528-7505
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	22
Issue	3
Pages	1914-1921
DOI	https://doi.org/10.1021/acs.cgd.1c01470

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