Upon visible-light irradiation, the heterogeneous polymer of PDI–Cu­(I)–PDI (PDI = perylene diimide) generates charge transfer states that are subsequently quenched by molecular oxygen for their participation in redox activity. This insoluble polymeric Cu­(I) is catalytically active for the oxidation of benzylic alcohols to corresponding aldehydes when suspended in dynamic micelles of PS-750-M. A broad substrate scope, excellent selectivity, and no over-oxidation reveal the catalyst robustness. The catalytic activity, control experiments, and time-dependent DFT calculations show the charge transfer states. The polymeric catalyst is entirely recyclable, as evidenced by the recycle studies using Scott’s recyclability test. The morphology, structure, copper’s oxidation state, and the catalyst’s thermal stability are determined by SEM, XPS, and TGA analysis.

The nanomaterial containing amphiphile-stabilized mononuclear Cu(II) is developed. The material is characterized by various spectroscopic techniques, such as X-ray absorption spectrscopy (XAS), high-resolution transmission electron microscopy, nuclear magnetic resonance (NMR), UV-vis, and infrared spectroscopies. Since the structural data for the amphiphile-bound Cu(II) center is not available, a theoretical model based on DFT calculations is employed. The analyses based on NMR spectroscopic data, including the isotope labeling, support that the tertiary amide group of the amphiphile binds to the Cu surface. Likewise, the bond distances found by XAS spectroscopy agree with the theoretical model. Time-dependent DFT studies predict that the low-lying excited state has a dominant ligand-to-metal charge transfer (LMCT) character. Cu(II) changes to Cu(I) assisted by the LMCT excitation upon visible light irradiation, generating robust catalytically active species. The catalytic activity for domino azidation-[3+2] cycloaddition reactions in water is investigated. The catalytic protocol is applicable on various substrates, and the catalytic material is stable under ambient conditions for up to three months.

A reversible Van der Waals complex formation between the electron‐deficient fluorinated aromatic ring and N,N‐dimethylformamide (DMF) molecules followed by light irradiation resulted in charge transfer (CT) process. The complex was stabilized by ammonium formate and further decomposed to form the C−N bond. Control experiments revealed that the simultaneous SNAr pathway also contributes to product formation. This methodology is mild, metal‐free, and effective for the amination of a variety of substrates. The reproducibility of this methodology was also verified on gram‐scale reactions. The CT states were supported by control UV/Vis spectroscopy and computational studies.

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