4.6 Article

Modulating vectored non-covalent interactions for layered assembly with engineerable properties

Journal

BIO-DESIGN AND MANUFACTURING
Volume 5, Issue 3, Pages 529-539

Publisher

SPRINGER HEIDELBERG
DOI: 10.1007/s42242-022-00186-3

Keywords

Vectored non-covalent interactions; Layered assembly; Supramolecular graphene; Engineerable properties; Physical vapor deposition

Funding

  1. Fund for Creative Research Groups of National Natural Science Foundation of China [51821093]
  2. National Natural Science Foundation of China [52175551, 52075484]
  3. National Key Research and Development Program [SQ2021YFE010405]
  4. Science Foundation Ireland (SFI) [15/CDA/3491, 12/RC/2275_P2]

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Supramolecular layered assembly is achieved by introducing different functional groups to the triazine skeleton using vectored non-covalent interactions, resulting in high stability and broad-spectrum fluorescence. Additionally, bio-inspired superhydrophobic pillar arrays can be constructed using aromatic interactions.
Vectored non-covalent interactions-mainly hydrogen bonding and aromatic interactions-extensively contribute to (bio)organic self-assembling processes and significantly impact the physicochemical properties of the associated superstructures. However, vectored non-covalent interaction-driven assembly occurs mainly along one-dimensional (1D) or three-dimensional (3D) directions, and a two-dimensional (2D) orientation, especially that of multilayered, graphene-like assembly, has been reported less. In this present research, by introducing amino, hydroxyl, and phenyl moieties to the triazine skeleton, supramolecular layered assembly is achieved by vectored non-covalent interactions. The planar hydrogen bonding network results in high stability, with a thermal sustainability of up to about 330 degrees C and a Young's modulus of up to about 40 GPa. Upon introducing wrinkles by biased hydrogen bonding or aromatic interactions to disturb the planar organization, the stability attenuates. However, the intertwined aromatic interactions prompt a red edge excitation shift effect inside the assemblies, inducing broad-spectrum fluorescence covering nearly the entire visible light region (400-650 nm). We show that bionic, superhydrophobic, pillar-like arrays with contact angles of up to about 170 degrees can be engineered by aromatic interactions using a physical vapor deposition approach, which cannot be realized through hydrogen bonding. Our findings show the feasibility of 2D assembly with engineerable properties by modulating vectored non-covalent interactions. [GRAPHICS] .

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