The Role of Spacers as a Probe in Variation of Photoluminescence Properties of Mono- and Bi-Nuclear Boron Compounds

Abstract

A series of N,O donor-based mono- and binuclear four-coordinated boron complexes were synthesized. Depending on the substitution and spacer, these complexes exhibit intense blue, green and yellow emission in solution states. Notably, the fluorescence quantum yields (ΦF) and fluorescence decay (lifetime, τ) of mononuclear boron complexes (2 a–2 e) were higher than the binuclear boron complexes (2 f–2 k). The lowest lifetime and quantum yield in binuclear boron complexes were due to intramolecular rotation induced non radiative processes. The disulphide spacer-based boron complexes 2 i–2 k showed aggregation-caused quenching in the THF/H2O mixture whereas no other complexes were ACQ responsive. These complexes show large Stokes shift, one of them i. e. 2 e has the highest Stokes shift of 130 nm. Further, the electrochemical study suggests the presence of two redox incidences. Theoretical studies show close corroboration between the TD-DFT computed and experimentally measured absorption maxima as well as DFT (GIAO) calculated and experimentally measured 11B NMR values. This complements the appropriate selection of the theoretical methods to shed light on the electronic transitions in the mono- and binuclear BF2 complexes. © 2024 Wiley-VCH GmbH.