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Abstract Supramolecular chemistry can transform organic synthesis by revealing that crystalline materials are not static but rather dynamic environments for controlled covalent bond formations and manipulations. This review focuses on how supramolecular chemistry can be developed to direct molecular synthesis in the organic solid state, directing reliable C─C bond formations to enable transformations difficult or impossible in solution. Special attention is given to postsynthetic modifications that serve to broaden the functional scope of solid‐state reactivity allowing organic crystals to be developed as molecular flasks and a form of supramolecular matter.
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This content will become publicly available on January 13, 2026
Context-Adaptive Nanotopology in Peptide Crystals
Biological systems, including proteins, employ water-mediated supramolecular interactions to adopt specific conformations for their functions. However, current solid-state supramolecular materials are typically stiff and fail to capture the dynamic behaviors observed in proteins. Here, we present dynamic crystal-hydrates of aliphatic dipeptides with sequence-isomers of leucine (L) and isoleucine (I). These crystals exhibit shallow conformational energy landscapes, with various reconfigurable crystal nano-architectures accessible through small changes in relative humidity and temperature. Specifically, for LI crystals, as water content changes, the solid-state supramolecular architecture rapidly and reversibly transitions between perpendicular and parallel honeycomb nano-architectures, as well as layered van der Waals structures, leading to significant and distinct variations in mechanical and photophysical properties. Our findings demonstrate the potential of leveraging aliphatic hydrophobic domains inspired by protein architectures to create dynamic solid-state materials with context-adaptive properties.
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- Award ID(s):
- 2410178
- PAR ID:
- 10573190
- Publisher / Repository:
- ChemRXiv
- Date Published:
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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