Tuning the Structure and Electronic Properties of B–N Fused Dipyridylanthracene and Implications on the Self-Sensitized Reactivity with Singlet Oxygen

Abstract

We demonstrate that the modification of anthracene with B ← N Lewis pairs at their periphery serves as a highly effective tool to modify the electronic structure with important ramifications on the generation and reactivity toward singlet oxygen. A series of BN-fused dipyridylanthracenes with Me groups in different positions of the pyridyl ring have been prepared via directed electrophilic borylation. The steric and electronic effects of the substituents on the structural features and electronic properties of the isomeric borane-functionalized products have been investigated in detail, aided by experimental tools and computational studies. We find that BDPA-2Me, with Me groups adjacent to the pyridyl N, has the longest B–N distance and shows overall less structural distortions, whereas BDPA-5Me with the Me group close to the anthracene backbone experiences severe distortions that are reflected in the buckling of the anthracene framework and dislocation of the boron atoms from the planes of the phenyl rings they are attached to. The substitution pattern also has a dramatic effect on the self-sensitized reactivity of the acenes toward O2 and the thermal release of singlet oxygen from the respective endoperoxides. Kinetic analyses reveal that BDPA-2Me rapidly reacts with O2, whereas BDPA-5Me is converted only very slowly to its endoperoxide. However, the latter serves as an effective singlet oxygen sensitizer, as demonstrated in the preferential formation of the endoperoxide of dimethylanthracene in a competition experiment. These results demonstrate that even relatively small modifications in the substitution of the pyridyl ring of BN-fused dipyridylanthracenes change the steric and electronic structure, resulting in dramatically different reactivity patterns. Our findings provide important guidelines for the design of highly effective sensitizers for singlet oxygen on one hand and the realization of materials that readily form endoperoxides in a self-sensitized manner and then thermally release singlet oxygen on demand on the other hand.

Threat to the Throne: Can Two Cooperating Boron Atoms Rival Transition Metals in Chemical Bond Activation and Catalysis?

“… [19] Concerning the reaction mechanism, the involvement of single‐electron transfer (SET) processes has been given consideration. The resulting B−O−O−B moiety resembles the B−Se−Se−B unit mentioned above and also Piers’ B−O−O−C endoperoxides, which were obtained from NHC‐stabilized 9‐boraanthracenes and O 2 [38–40] . Likewise, a C 6 H 6 solution of Kinjo's 1,4,2,5‐diazadiborinine 6 reacts with neat O 2 to form the endoperoxide 15 (Scheme 7).…”

Singlet oxygen stimulus for switchable functional organic cages

“…To date, this reversible reaction on DPA was mainly employed for the sensing or delivery of 1 O 2 with a few reports of fatigue over several cycles. 11,12 …”

B←N Coordination: From Chemistry to Organic Photovoltaic Materials

“…Reproduced with permission. [ 75,83,87,88 ] Copyright 2006, Wiley; Copyright 2018, Elsevier; Copyright 2017 and 2019, American Chemical Society.…”