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Updated: May 31, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
Pathway Complexity in Naphthalene Diimide Supramolecular Polymers: Interruption by an Aromatic Solvent
Yun Huang1, Chengyu Shi2, Ruilong Zhang3
1School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, Anhui, People's Republic of China.
Abstract:
Solvents critically influence supramolecular assembly pathways, providing a straightforward strategy to steer structural outcomes without complex synthetic modifications. Here, by regulating solvent composition and employing synchrotron-based x-ray absorption spectroscopy, we elucidate how toluene (Tol) disrupts the continuous assembly of a naphthalene diimide (NDI) derivative. In methylcyclohexane, the system follows a sequential pathway from metastable nanoparticles to nanofibers. Introducing Tol interrupts this progression, stabilizing the nanoparticles as the sole product. Oxygen K-edge X-ray absorption spectroscopy analysis indicates that Tol selectively suppresses intermolecular hydrogen bonding via π-π interactions while leaving intramolecular hydrogen bonds (HBs) intact. These insights, framed through solute-solvent π-interactions, advance the concept of "solvent engineering" for rationally programming assembly pathways and functional architectures.
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