Introducing Perylene as a New Member to the Azaborine Family

Abstract

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‐Br 2 DBA(OH) 2 . A Stille‐type reaction first furnishes the alkynyl‐substituted species 1,5‐(RCC) 2 DBA(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(SiMe 3 ) 2 leads to aminoborane intermediates 1,5‐(RCC) 2 DBA(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, t BuPh) can be introduced at the 2/8 positions of the perylene core. The products obtained undergo reversible reduction and are efficient blue/turquoise emitters.