Stoichiometry validation of supramolecular complexes with a hydrocarbon cage host by van ’t Hoff analyses

• Published in: Nature communications Vol. 14; no. 1; pp. 8246 - 8
• Main Authors: Fukunaga, Toshiya M., Onaka, Yuzuka, Kato, Takahide, Ikemoto, Koki, Isobe, Hiroyuki
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 21.12.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 639/301/923/3931; 639/301/923/966; 639/638/541/966; Bonding strength; Cages; Chemical reactions; Chloroform; Curve fitting; Humanities and Social Sciences; Hydrocarbons; Hydrogen bonding; Hydrogen bonds; Information theory; multidisciplinary; Science; Science (multidisciplinary); Stoichiometry; Titration
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-43979-5

Defining chemical processes with equations is the first important step in characterizing equilibria for the assembly of supramolecular complexes, and the stoichiometry of the assembled components must be defined to generate the equation. Recently, this subject has attracted renewed interest, and statistical and/or information-theoretic measures were introduced to examine the validities of the equilibrium models used during curve fitting analyses of titration. The present study shows that these measures may not always be appropriate for credibility examinations and that further reformation of the protocols used to determine the overall stoichiometry is necessary. Hydrocarbon cage hosts and their chloroform complexes formed via weak CH-π hydrogen bonds were studied, which allowed us to introduce van ’t Hoff analyses for effective validation of the stoichiometries of supramolecular complexes. This study shows that the stoichiometries of supramolecular complexes should be carefully examined by adopting multiple measures with different origins. “van ’t Hoff, the first Nobel laureate, invented a double-arrow formalism to define equilibria in 1884. Here, the authors apply his accompanying method, the van ’t Hoff plot, to a modern problem to decide the stoichiometry of supramolecular complexes.”