Substitutional doping of perylene with two boron atoms at the 6b/12b positions and two oxygen or nitrogen atoms at the 1/7 positions has been achieved. The modular synthesis route developed for these bis‐BO‐ (3) and bis‐BN‐perylenes (5) starts from the readily accessible borinic acid derivative of the doubly brominated 9,10‐dihydro‐9,10‐diboraanthracene (DBA), 1,5‐Br2DBA(OH)2. A Stille‐type reaction first furnishes the alkynyl‐substituted species 1,5‐(RCC)2DBA(OH)2 (2), which undergo double ring closure to afford 3 via the gold‐catalyzed addition of the O−H bonds to the C≡C bonds. Treatment of 2 with MeN(SiMe3)2 leads to aminoborane intermediates 1,5‐(RCC)2DBA(N(H)Me)2, which can be ring‐closed to give 5 in a similar manner as in the case of 3. Different substituents R (such as Me, tBuPh) can be introduced at the 2/8 positions of the perylene core. The products obtained undergo reversible reduction and are efficient blue/turquoise emitters.

The isoelectronic replacement of C=C bonds with ‒B=N+ bonds in polycyclic aromatic hydrocarbons (PAHs) is a widely used tool to prepare novel optoelectronic materials. Far less well explored are corresponding...

A series of fluorinated triaryl borates B(OArF)3 (ArF = 2-FC6H4, 3-FC6H4, 4-FC6H4, 2,4-F2C6H3, 3,5-F2C6H3, 2,3,4-F3C6H2, 2,4,6-F3C6H2, 3,4,5-F3C6H2) have been prepared and isolated from the reactions of the mono-, di-, or...

Vicinally diiodinated polycyclic aromatic hydrocarbons (I2‐PAHs) are accessible from the corresponding diborylated B2‐PAHs through boron/iodine exchange. The B2‐PAHs have been prepared via twofold electrophilic borylation reactions templated by a vicinally disilylated benzene. Our protocol is applicable to fluorenes, acenes, annulated acenes, oligoaryls, and even [5]helicene. Using B2‐naphthalene as the example, we have shown that the reaction scope can, in principle, be expanded to include the synthesis of vicinally dibrominated and dihydroxylated PAHs. The usefulness of the building blocks provided by our method in the field of optoelectronic materials was demonstrated by the successful conversion of I2‐fluoranthene to the analogous doubly alkynylated fluoranthene emitter.

Herein we report the B(3,4,5-F3H2C6)3-catalysed C3-allylation of indoles using allylic esters. 25 examples of C3-allylated products are presented in up to 97% yield. The mechanism for the reaction was explored...