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A new family of unsymmetrical boron chromophores chelated with two BF2 units, named BOPAM, has been developed via a one‐pot, three‐step reaction starting from commercially available thioamides via i) conversion to amidrazones, ii) condensation with pyrrole aldehydes, and iii) boron chelation. This synthetic pathway has been proven to be highly efficient, having a broad substrate tolerance and giving the BOPAM products high yield. Notably, some of the BOPAM dyes show interesting photophysical properties with fluorescence quantum yields up to 0.98 in toluene. A fine‐tuning of their emissive properties has been attained through tailored molecular design strategies guided by in‐depth computational investigations. Tailored substitution with electron‐donating groups at the BOPAM ring leads to the opening of a non‐radiative decay channel involving a dark state and consequently a significant quenching of the fluorescence. The study is complemented by exhaustive steady‐state and time‐resolved spectroscopic measurements. [ABSTRACT FROM AUTHOR]

A novel category of asymmetric boron chromophores with the attachment of two BF2 moieties denoted as BOPAM, has been successfully synthesized via a one-pot three-step reaction starting from N-phenylbenzothioamide. This synthetic route results in the production of [a] and [b]benzo-fused BOPAMs along with post-functionalization of the [a]benzo-fused BOPAMs. The photophysical properties of these compounds have been systematically investigated through steady-state absorption and fluorescence emission measurements in solvents at both ambient and cryogenic temperatures, as well as in the solid state. Computational methods have been employed to elucidate the emissive characteristics of the benzo-fused BOPAMs, revealing distinctive photophysical attributes, including solvent-dependent fluorescence intensity. Remarkably, certain BOPAM derivatives exhibit noteworthy photophysical phenomena, such as the induction of off-on fluorescence emission under specific solvent conditions and the manifestation of intermolecular charge transfer states in solid-state matrices. Through post-functionalization strategies involving the introduction of electron-donating groups onto the [a]benzo-fused BOPAM scaffold, an intramolecular charge transfer (ICT) pathway is activated, leading to substantial fluorescence quenching via non-radiative decay processes. Notably, one [a]benzo-fused BOPAM variant exhibits a pronounced fluorescence enhancement upon exposure to acidic conditions, thereby underscoring its potential utility in pH-sensing applications., (© 2024 Wiley‐VCH GmbH.)