Orthogonal halogen (X)-bonding and hydrogen (H)-bonding have been employed for constructing a surface functionalizable supramolecular polymer in water featuring tunable morphology and dual stimuli (pH and temperature) responsive properties.

Supra-amphiphiles constituted of noncovalent bonds have emerged as attractive systems for fabrication of stimuli-responsive self-assembled nanostructures. A unique supramolecular strategy utilizing halogen (X)-bonding interaction has been demonstrated for constructing emissive supra-π-amphiphiles in water from a hydrophobic pyridyl functionalized naphthalene monoimide (NMI-Py) based X-bond acceptor and hydrophilic iodotetrafluorophenyl functionalized polyethylene glycol (PEG-I) or triethylene glycol (TEG-I) based X-bond donors, while their luminescent higher ordered assemblies were governed by orthogonal dipole−dipole interaction and π-stacking of the NMI-Py fluorophore as probed by SCXRD and DFT calculations. Control molecules lacking iodotetrafluorophenyl moiety at the polyethylene glycol chain end failed to create any defined morphology from the NMI-Py, suggesting X-bonding is prerequisite for the nanostructure formation. Variation in the chain length of the X-bond donors leads to different morphologies (fiber vs vesicle) for PEG-I and TEG-I. Acid triggered denaturing of the X-bonds caused pH responsive disassembly of the thermally robust nanostructures. This strategy paves the way for facile fabrication of structurally diverse smart and adaptive luminescent functional materials with tunable morphology.

This article reports π-chromophore assemblies from three structurally related dipolar naphthalene monoimide (NMI) luminogens (M1, M2 and M3) by underexplored orthogonal dipole-dipole interaction and halogen bonding. Single crystal structure analysis...

Supramolecular polymers have emerged as attractive systems for construction of responsive and adaptive smart materials. In this context, halogen (X)-bonding is relatively underexplored. The present work describes a X-bonded supramolecular...