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Abstract We report on a dendronized bis‐urea macrocycle1self‐assembling via a cooperative mechanism into two‐dimensional (2D) nanosheets formed solely by alternated urea‐urea hydrogen bonding interactions. The pure macrocycle self‐assembles in bulk into one‐dimensional liquid‐crystalline columnar phases. In contrast, its self‐assembly mode drastically changes in CHCl₃or tetrachloroethane, leading to 2D hydrogen‐bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick‐like hydrogen bonding pattern between bis‐urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non‐covalent interaction motif, which is of great interest for materials development. 

Manipulations of nanocrystal (NC) surfaces have propelled the applications of colloidal NCs across various fields such as bioimaging, catalysis, electronics, and sensing applications. In this Feature Article, we discuss the surface chemistry of colloidal NCs, with an emphasis on semiconductor quantum dots, and the binding motifs for various ligands that coordinate NC surfaces. We present isothermal titration calorimetry (ITC) as a viable technique for studying the thermodynamics of the ligand association and exchange at NC surfaces by discussing its principles of operation and highlighting results obtained to date. We give an in-depth description of various thermodynamic models that can be used to interpret NC–ligand interactions as measured not only by ITC, but also by NMR, fluorescence quenching, and fluorescence anisotropy techniques. Understanding the complexity of NC surface–ligand interactions can provide a wide range of avenues to tune their properties for desired applications.