Evidence for Borylene Carbonyl (LHB═C═O) and Base-Stabilized (LHB═O) and Base-Free Oxoborane (RB≡O) Intermediates in the Reactions of Diborenes with CO2.

Doubly N-heterocyclic-carbene-stabilized diborenes undergo facile reactions with CO2, initially providing dibora-ß-lactones. These lactones convert over time to their 2,4-diboraoxetan-3-one isomers through a presumed dissociative pathway and hypovalent boron species borylene carbonyls (LHB═C═O) and base-stabilized oxoboranes (LHB═O). Repeating these reactions with doubly cyclic(alkyl)(amino)carbene-stabilized diborenes allowed the isolation of a borylene carbonyl intermediate, whereas a base-stabilized oxoborane could be inferred by the isolation of a boroxine from the reaction mixture. These results, supported by calculations, confirm the presumed mechanism of the diboralactone-to-diboraoxetanone isomerization while also establishing a surprising level of stability for three unknown or very rare hypovalent boron species: base-stabilized derivatives of the parent borylene carbonyl (LHB═C═O) and parent oxoborane (LHB═O) as well as base-free oxoboranes (RB≡O).

Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning.

In this combined experimental and theoretical study, a computational protocol is reported to predict the excited states in D-π-A compounds containing the B(FXyl)2 (FXyl = 2,6-bis(trifluoromethyl)phenyl) acceptor group for the design of new thermally activated delayed fluorescence (TADF) emitters. To this end, the effect of different donor and π-bridge moieties on the energy gaps between local and charge-transfer singlet and triplet states is examined. To prove this computationally aided design concept, the D-π-B(FXyl)2 compounds 1-5 were synthesized and fully characterized. The photophysical properties of these compounds in various solvents, polymeric film, and in a frozen matrix were investigated in detail and show excellent agreement with the computationally obtained data. Furthermore, a simple structure-property relationship is presented on the basis of the molecular fragment orbitals of the donor and the π-bridge, which minimize the relevant singlet-triplet gaps to achieve efficient TADF emitters.

An Iterative Divergent Approach to Conjugated Starburst Borane Dendrimers.

Using a new divergent approach, conjugated triarylborane dendrimers were synthesized up to the 2nd generation. The synthetic strategy consists of three steps: 1) functionalization, via iridium catalyzed C-H borylation; 2) activation, via fluorination of the generated boronate ester with K[HF2 ] or [N(nBu4 )][HF2 ]; and 3) expansion, via reaction of the trifluoroborate salts with aryl Grignard reagents. The concept was also shown to be viable for a convergent approach. All but one of the conjugated borane dendrimers exhibit multiple, distinct and reversible reduction potentials, making them potentially interesting materials for applications in molecular accumulators. Based on their photophysical properties, the 1st generation dendrimers exhibit good conjugation over the whole system. However, the conjugation does not increase further upon expansion to the 2nd generation, but the molar extinction coefficients increase linearly with the number of triarylborane subunits, suggesting a potential application as photonic antennas.