Hydrogen-bonding interactions play an important role in many chemical and biological systems. Fluorine acting as a hydrogen-bond acceptor in intermolecular and intramolecular interactions has been the subject of many controversial discussions and there are different opinions about it. Recently, we have proposed a correlation between the propensity of fluorine to be involved in hydrogen bonds and its (19)F NMR chemical shift. We now provide additional experimental and computational evidence for this correlation. The strength of hydrogen-bond complexes involving the fluorine moieties CH2F, CHF2, and CF3 was measured and characterized in simple systems by using established and novel NMR methods and compared to the known hydrogen-bond complex formed between acetophenone and p-fluorophenol. Implications of these results for (19)F NMR screening are analyzed in detail. Computed values of the molecular electrostatic potential at the different fluorine atoms and the analysis of the electron density topology at bond critical points correlate well with the NMR results.

assembled and non-assembled systems and offer a robust set of independent tools to highlight atomic details in self-organized structures.

The self‐assembly of N,N′,N″‐trialkylbenzene‐1,3,5‐tricarboxamides (BTAs) 1 or of “crowded” BTAs 11 and 12 lead to supramolecular columnar‐stacked structures with attractive material properties. The introduction of three alkoxy groups is reported to reinforce the self‐assembly process. The influence of a single substituent introduced onto the aromatic core of BTA significantly affects the self‐assembly process. The aggregation process of 2‐substituted BTAs in the bulk and in solution, as studied by DSC, POM, X‐ray diffraction and 1H NMR experiments, is impaired by hydrogen‐bond‐accepting substituents but strengthened by non‐hydrogen‐bond‐accepting substituents.