Two-Dimensional Reversible Supramolecular Polymorphism Governed by Weak Solvent

Article Article scientifique Article Two-Dimensional Reversible Supramolecular Polymorphism Governed by Weak Solvent–Solute Interactions eng 2025-11-08 author Paul Subhankar author Li Zihan 419426 Chimie physique (groupe 8) (CHIF8) author Biswas Sagar author Biswas Debjit author Dey Arka B. author Besnard Céline 0000-0001-5699-9675 682138 Administration de la section de chimie (CHIAD) author Adachi Takuji 0000-0002-0577-1926 930973 Département de chimie physique (CHIFI) author Manjunatha Reddy G. N. 0000-0002-8283-2462 author Chaudhuri Debangshu 0000-0002-8941-4327 5c02446 10.1021/acs.chemmater.5c02446 0897-4756 https://pubs.acs.org/doi/10.1021/acs.chemmater.5c02446 Molecular self-assembly can be a powerful strategy for fabricating dynamic two-dimensional (2D) nanomaterials. However, formulating a rational design principle that meets the stringent thermodynamic and kinetic requirements for uniform in-plane growth, while also allowing dynamic structural rearrangement, presents a considerable challenge. We report a hydrophobic core-substituted naphthalenediimide that self-assembles in water−dioxane mixtures to form a pair of 2D polymorphs, with distinct morphological, optical, and surface characteristics. Changing the solvent composition or temperature prompts an in situ transformation between the two polymorphs in solution. A comprehensive structural investigation using solid-state NMR spectroscopy, X-ray, and electron diffraction analyses reveals not only the nature of molecular packing and noncovalent (n → π* and π-stacking) interactions stabilizing each 2D polymorph but also the role of weak solvent−solute interactions in driving polymorphic interconversion. Variations in the perfluoroalkyl side chains arrangements on the exposed 2D surface of the two polymorphs lead to distinct solvent−solute interactions at the solid−liquid interface, which affects the surface free-energy and relative stability in different solvent compositions. Further, the entropy change associated with surface ordering of perfluoroalkyl side chains and desolvation dictates thermal reorganization between the polymorphs. How changes in dioxane−water microheterogeneity with solution composition and temperature may affect these weak solvent−solute interactions and the phase equilibrium is also discussed. Dewey 540 Department of Science and Technology, Ministry of Science and Technology, India I-20221016 38 Département de chimie physique 142 false 1393 Groupe Adachi Chemistry of materials d5c40267-8a44-4acd-8056-74c85ed7176a Article (Accepted version) Public 2D-Manuscript-R3.pdf 1845742 application/pdf Restricted 2026-11-09 7b6822c96883f123ef9bf602452114b7964f86352d9ad4fb7a44cfb03d534c8c 48c8cc11-f8f0-4bb4-b660-5a66a45bf482 Article (Published version) Restricted two-dimensional-reversible-supramol.pdf 7391549 application/pdf c270b5ca429079c3d3bad494e643e07c21497954b52f0de86de6f53d62662cbd embargoedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

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