High aspect ratio nanotubes assembled from macrocyclic iminium salts

Sun, Chao; Shen, Meng; Chavez, Anton D.; Evans, Austin M.; Liu, Xiaolong; Harutyunyan, Boris; Flanders, Nathan C.; Hersam, Mark C.; Bedzyk, Michael J.; Olvera de la Cruz, Monica; Dichtel, William R.

doi:10.1073/pnas.1809383115

Title: High aspect ratio nanotubes assembled from macrocyclic iminium salts

Journal Article · Tue Aug 21 00:00:00 EDT 2018 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1809383115· OSTI ID:1465619

; Shen, Meng; Chavez, Anton D.; Evans, Austin M.;

; Harutyunyan, Boris; Flanders, Nathan C.; Hersam, Mark C.;

;

One-dimensional nanostructures such as carbon nanotubes and actin filaments rely on strong and directional interactions to stabilize their high aspect ratio shapes. This requirement has precluded making isolated, long, thin organic nanotubes by stacking molecular macrocycles, as their noncovalent stacking interactions are generally too weak. Here we report high aspect ratio (>10³), lyotropic nanotubes of stacked, macrocyclic, iminium salts, which are formed by protonation of the corresponding imine-linked macrocycles. Iminium ion formation establishes cohesive interactions that, in organic solvent (tetrahydrofuran), are two orders of magnitude stronger than the neutral macrocycles, as explained by physical arguments and demonstrated by molecular dynamics simulations. Furthermore, nanotube formation stabilizes the iminium ions, which otherwise rapidly hydrolyze, and is reversed and restored upon addition of bases and acids. Acids generated by irradiating a photoacid generator or sonicating chlorinated solvents also induced nanotube assembly, allowing these nanostructures to be coupled to diverse stimuli, and, once assembled, they can be fixed permanently by cross-linking their pendant alkenes. As large macrocyclic chromonic liquid crystals, these iminium salts are easily accessible through a modular design and provide a means to rationally synthesize structures that mimic the morphology and rheology of carbon nanotubes and biological tubules.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Cornell Materials Research Science and Engineering Center; US Army Research Office (ARO); National Science Foundation (NSF); Northwestern University; National Defense Science and Engineering Graduate Fellowship

Grant/Contract Number:: AC02-06CH11357; FG02-08ER46539; W911NF-15-1-0447

OSTI ID:: 1465619

Alternate ID(s):: OSTI ID: 1504967

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 115 Journal Issue: 36; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 25 works

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Title: High aspect ratio nanotubes assembled from macrocyclic iminium salts

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