Continuous variation method, known as Job plot, is the most commonly applied method for the determination of stoichiometry of complex chemical entities for over 100 years. Although, the method was proven successful in the analysis of very stable metal–ligand complexes, we demonstrate that its use in supramolecular chemistry often provides false results. We support this statement with multiple simulations as well as cases studies of several real host–guest systems. We propose an alternative, general method relying on the analysis of residual distribution in titration data fitting. The latter method is more convenient compared to the Job plot and unlike it gives correct results in all real cases studied.

Herein, we report that thermal Z→E isomerisation of simple azobenzene urea derivatives is selectively and predictably controlled by anion binding. The rate of this process depends strictly on the anion concentration and its binding affinity to the Z-isomer of the azobenzene host, i.e. increased rate constants are observed for higher anion concentration as well as for more strongly bound guests. The origin of this phenomenon is attributed to the electron density transfer from the anion to the host π-system, resulting in increased repulsion between the lone electron pairs in the NN bond.

Searching for regularities in the large set of structurally diverse macrocyclic probes allowed us to determine the structural requirements for the selective recognition of chloride over more basic anions such as H₂PO₄⁻ or RCO₂⁻ by a putative anion receptor.