Pyrrolo[2,3-d:5,4-d′]bisthiazoles: Alternate Synthetic Routes and a Comparative Study to Analogous Fused-Ring Bithiophenes

Abstract

New synthetic methods have been developed for the preparation of 4-alkyl- and 4-aryl-pyrrolo[2,3-d:5,4-d']bisthiazole (PBTz) building blocks from 2,4-thiazolidinedione. The resulting PBTz products have been fully characterized via structural, electronic, and optical methods, thus allowing full comparison to the previously reported dithieno[3,2-b:2',3'-d]pyrrole (DTP) analogues. Such comparisons then allow a detailed discussion of the relative electronic effects of the various methods utilized to tune the properties of the parent DTP building block.

Dithienothiophenes at Work: Access to Mechanosensitive Fluorescent Probes, Chalcogen-Bonding Catalysis, and Beyond

“…66 in electron transport materials as part of co-polymers or centered between two NDIs. [72][73][74][75] Compared to DTPs such as 51 (Figure 7), the nitrogen bridge in 105 decreases the LUMO levels significantly (-0.8 eV) and shifts the absorption slightly to the red. 86 The addition of electron withdrawing cyano substituents in the bridge of 120 and the installation of peripheral sulfur redox switches provides access to sulfoxides 121 and sulfones 122.…”

“…This study covers also the selenium homologue 104 for the same purpose . Pyrrolo­[2,3- d :5,4- d ′]­bisthiazoles 105 have been explored quite extensively for use in electron transport materials as part of copolymers or centered between two NDIs. − Compared to DTPs such as 51 (Figure ), the nitrogen bridge in 105 decreases the LUMO levels significantly (−0.8 eV) and shifts the absorption slightly to the red.…”

Magnetic ordering in a vanadium-organic coordination polymer using a pyrrolo[2,3-d:5,4-d′]bis(thiazole)-based ligand

“…This analysis is consistent with recently published results. 27 Analysis of the crystal packing in 5 reveals the existence of two short intermolecular contacts, N(1)⋯S(2) (3.109(5) Å) and N(3)⋯S(2) (3.083(5) Å), which link molecules into layers parallel to the ab plane ( Fig. 2b ).…”

Chalcogen Bridged Thieno- and Selenopheno[2,3-d:5,4-d′]bisthiazole and Their Diketopyrrolopyrrole Based Low-Bandgap Copolymers

“…11,17−19 In addition, our research group and others have reported the effects of introducing a nitrogen atom to bridge the thiazole units to afford the fused building block pyrrole [2,3-d:5,4-d′]bisthiazole (PBTz) (Figure 1). 20−23 We note here our gratitude to Rasmussen et al 23 for highlighting that our earlier publications had used the incorrect IUPAC name. The bridged architecture has significant effects on the electronic and structural properties of the polymer main chain.…”

“…34 The detailed synthesis of 4,4′-dibromo-2,2′bis(triisopropylsilyl)-5,5′-bithiazole (3) is reported in our previously published work. 16,20,23 The new comonomers 8 and 9 were synthesized in three steps from monomer 3. Stille coupling of 3 with precursors 1 and 2 in toluene at 170 °C afforded compounds 4 and 5 in moderate yields (35−36%).…”