Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

Llorenç Rubert; Md Faizul Islam; Andrew B. Greytak; Rahul Prakash; Mark D. Smith; Rosa Maria Gomila; Antonio Frontera; Linda S. Shimizu; Bartolome Soberats

doi:10.1002/anie.202312223

Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

Llorenç Rubert, Md Faizul Islam, Andrew B. Greytak, Rahul Prakash, Mark D. Smith, Rosa Maria Gomila, Antonio Frontera, Linda S. Shimizu, Bartolome Soberats

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl₃ or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.

Original language	English
Article number	e202312223
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	46
DOIs	https://doi.org/10.1002/anie.202312223
State	Published - Nov 13 2023

Funding

We thank J. Cifre, A. Busquets, F. Hierro, and G. Martorell of the Serveis Cientificotènics (SCT) of the UIB for their technical support. We acknowledge the MICINN/AEI of Spain (Projects PID2019‐107779GA‐I00/AEI/10.13039/501100011033, EQC2018‐004206‐P, RED2018‐102331‐T, TED2021‐130946B‐100, CNS2022‐135945) and the GOIB (AAEE 116/2017, AP_2021_042) and the National Science Foundation (CHE‐2203830, CHE‐1904386, CHE‐2109064) for financial support. We thank GOIB for cofinancing the TEM instrument with “FEDER, Una manera de hacer Europa” resources. B. S. is thankful to the MICINN/AEI for the “Ramón‐y‐Cajal” fellowship (RYC‐2017‐21789). L. R. is thankful to Govern de les Illes Balears for the PhD fellowship (FPI_039_2020). We thank J. Cifre, A. Busquets, F. Hierro, and G. Martorell of the Serveis Cientificotènics (SCT) of the UIB for their technical support. We acknowledge the MICINN/AEI of Spain (Projects PID2019-107779GA-I00/AEI/10.13039/501100011033, EQC2018-004206-P, RED2018-102331-T, TED2021-130946B-100, CNS2022-135945) and the GOIB (AAEE 116/2017, AP_2021_042) and the National Science Foundation (CHE-2203830, CHE-1904386, CHE-2109064) for financial support. We thank GOIB for cofinancing the TEM instrument with “FEDER, Una manera de hacer Europa” resources. B. S. is thankful to the MICINN/AEI for the “Ramón-y-Cajal” fellowship (RYC-2017-21789). L. R. is thankful to Govern de les Illes Balears for the PhD fellowship (FPI_039_2020).

Keywords

2D Polymers
Hydrogen Bonding
Liquid Crystals
Macrocycles
Self-Assembly

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10.1002/anie.202312223

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title = "Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network",

abstract = "We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl3 or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.",

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AU - Prakash, Rahul

AU - Smith, Mark D.

AU - Gomila, Rosa Maria

AU - Frontera, Antonio

AU - Shimizu, Linda S.

AU - Soberats, Bartolome

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AB - We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl3 or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.

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Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

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