Isomerically Pure Star‐Shaped Triphenylene–Perylene Hybrids Involving Highly Extended π‐Conjugation

Abstract

The synthesis and characterization of a new type of a highly conjugated heterocyclic π‐chromophore, consisting of a central triphenylene core fused with three perylene monoimide units (star‐shaped molecules), is described. By judicious bay functionalization with tert‐butylphenoxy substituents, aggregation was completely prevented by using 1,1,2,2‐tetrachloroethane, allowing for a straightforward purification and, for the very first time, the complete separation of the constitutional isomers by HPLC. Both isomers can be easily distinguished by means of several conventional spectroscopic techniques. Furthermore, we have illustrated the absence of supramolecular aggregates and enhanced processability by noncovalent functionalization of graphene substrates, showing an outstanding homogeneity and demonstrating a different doping behavior in both isomers, making it possible to distinguish them by Raman spectroscopy.

Progress in the synthesis of perylene bisimide dyes

“…30 Subsequent condensation with aliphatic or aromatic primary amines under varied reaction conditions afforded the desired tetrachloro-PBIs 22a-d,g-n in moderate to excellent yields depending on the amine and the synthetic protocol. 25,[54][55][56][58][59][60][61] In general, the reaction with aromatic amines requires harsher conditions, such as higher temperatures and prolonged time (e.g. synthesis of 22j versus 22k).…”

Diastereoselective formation of homochiral flexible perylene bisimide cyclophanes and their hybrids with fullerenes

“…Scheme 1 shows the synthetic procedure of cyclophanes starting from N,N 0 -dihydroxypropyl-1,6,7,12-tetrakis-(4-tertbutylphenoxy)-3,4:9,10-perylenetetracarboxydiimide 1, which was prepared in a two-step synthesis according to modied literature procedures. 26,27 Cyclization of 1 28,29 with malonyl dichloride using pyridine 30 as a base provides P2, P3, and P4 as purple solids in 8.1%, 3.4%, and 1.3% yields, respectively. 2-4 indicate the associated number of PBIs (P) in the ring.…”

Noncovalent Functionalization and Passivation of Black Phosphorus with Optimized Perylene Diimides for Hybrid Field Effect Transistors

“…This is useful for improving the surface coating, allowing for a denser and more structured packing of the molecules (Scheme 1). [55] In addition, we compared these molecules with the N-bis-(tert-butyl-(2,2′-aminobutylazanediyl)-diacetate)-3,4,9,10-perylene diimide derivative previously reported by our group, which serves as an appropriate control experiment. [42,49] Hence, according to Scheme 2, the synthetic approach started from the perylene-3,4,9,10-tetracarboxylic dianhydride (a).…”

“…[ 54 ] Commonly, solvents such as chloroform, ortho‐dichlorobenzene or dimethylsulphoxide (DMSO) are used for solubilizing perylenes (Figure S4, Supporting Information). [ 55 ] Moreover, our group previously reported the formation of labile charge transfer complexes (CTC) between perylene diimides and electron donating solvents like pyrrolidones or DMSO. [ 42 ] In this sense, THF is very convenient for the noncovalent functionalization of BP because it avoids the formation of CTCs under inert conditions, while allowing the spectroscopic characterization without extrinsic interferences.…”