Cyclopentannulation and cyclodehydrogenation of isomerically pure 5,11-dibromo-anthradithiophenes leading to contorted aromatics

Abstract

Isomerically pure 5,11-dibromo-ADT was used to create contorted aromatics with large splay angles, low band gaps, and low LUMOs.

Synthesis of anthradithiophene containing conjugated polymers via a cross-coupling strategy

“…These metal catalyzed transformations were possible owing to our recent report of a soluble and isomerically pure 5,11-dibromodihexylanthradithiophene 5 (Scheme 1). 25 The halogenated ADT monomer provides alternative reaction pathways to enlarge the library of possible coupling partners and to expand the possible aryl substituents (e.g., ester groups) that would not be compatible with the traditional nucleophilic substitutions pathway. An initial version of this work was deposited to ChemRxiv on July 23, 2020.…”

Donor‐acceptor copolymers from cyclopentannulation polymerizations with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm] perylene acceptors

“…While molecular systems with 1,6-dibromoanthracene as the aromatic precursor has been developed the most, 13,[24][25][26][27] we and others have also investigated small molecule systems based on higher acenes, anthradithiophene, and pyrene. [28][29][30][31] In this work, we have extended the cyclopentannulation polymerization chemistry to include monomers based on 1,6-dibromopyrene and 3,9-dibromoperylene. These monomers open new possibilities to further tune frontier orbital energies of CP-PAH based copolymers over a broad range and give access to unique carbon rich materials.…”

“…The palladium‐catalyzed annulation chemistry employed here is an efficient ring forming reaction that we have utilized to create both small molecule and polymeric materials. While molecular systems with 1,6‐dibromoanthracene as the aromatic precursor has been developed the most, 13,24–27 we and others have also investigated small molecule systems based on higher acenes, anthradithiophene, and pyrene 28–31 . In this work, we have extended the cyclopentannulation polymerization chemistry to include monomers based on 1,6‐dibromopyrene and 3,9‐dibromoperylene.…”

Synthesis of Anthradithiophene Containing Conjugated Polymers via a Cross-coupling Strategy

“…These metal catalyzed transformations were possible owing to our recent report of a soluble and isomerically pure 5,11-dibromodihexylanthradithiophene 5 (Scheme 1). 20 The halogenated ADT monomer provides alternative reaction pathways to enlarge the library of possible coupling partners and to expand the possible aryl substituents (e.g., ester groups) that would not be compatible with the traditional nucleophilic substitutions pathway. An initial version of this work was deposited to ChemRxiv on July 23, 2020.…”