6,6'-Biazulenic core as a platform for unlocking Hammett constants <i>via</i> electrochemical free-energy relationships.

ABSTRACT: Quantitative appreciation of electronic substituent effects is beneficial across the chemical sciences, from reaction kinetics and catalysis to functional materials design and enzymatic processes. While Hammett parameters (σ constants) constitute the most widely invoked paradigm, their determination for structurally complex functional groups is often impractical by traditional empirical means. Herein, we demonstrate that the reversible one-step, 2-e^- reduction of linearly functionalized 1,1',3,3'-tetraethoxycarbonyl-6,6'-biazulene provides a simple electrochemical readout of effective Hammett constants. By design, the values obtained align closely with the conventional σ _p descriptors pertaining to benzenoid systems. This approach not only helps reevalua

SUBMITTER: Mandigo JA 

PROVIDER: S-EPMC12893891 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature