N‐Annulated Perylene Bisimides to Bias the Differentiation of Metastable Supramolecular Assemblies into J‐ and H‐Aggregates

Abstract

The unique self‐assembling features of N‐annulated perylene bisimides (PBIs) 1 and 2 are reported. The stability of the aggregates of diester 1, in which no H‐bonding interactions are operative, corroborates the significance of long‐range van der Waals and dipole–dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups within the N‐annulated PBI in 2 stimulates pathway differentiation to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions. The results presented demonstrate unprecedented levels of control over synthetic supramolecular self‐assembly and the rich differentiation that N‐annulated PBIs exhibit, opening the door to new, complex, functional supramolecular materials.

Modulating the Differentiation of Kinetically Controlled Supramolecular Polymerizations through the Alkyl Bridge Length

“…A detailed investigation of the supramolecular polymerization mechanism has been performed by utilizing variable temperature (VT) UV/Vis spectroscopy in MCH as solvent. Noteworthy, these VT‐UV/Vis studies carried out with N‐PBI 1 showed the formation of up to three J ‐type aggregated species [11] . In the case of 2 – 4 , pristine MCH could not be used since, unlike 1 , heating up the diluted solutions of these N‐PBIs up to 90 °C did not result in the characteristic UV/Vis spectra ascribable to perylene‐based monomeric species with two intense bands at λ=486 and 519 nm, corresponding to the A 0‐1 /A 0‐0 transitions, [16] i.e.…”

“…Similarly to compound 1 , [11] N‐PBIs 2 – 4 were synthesized in a multistep protocol starting from commercially available perylene‐3,4,9,10‐tetracarboxylic dianhydride, methyl 3,4,5‐trihydroxybenzoate and propane‐1,3‐diamine, putrescine, and cadaverine for 2 , 3 , and 4 , respectively (for details on synthesis and characterization, see the Supporting Information).…”

“…To decrease the high stability of the aggregated species formed by 2 – 4 , we have utilized a MCH/Tol 1/1 mixture as solvent. It is worth mentioning that, in these solvent conditions, compound 1 is able to form four different aggregates species, too [11] …”

From Oligo(Phenyleneethynylene) Monomers to Supramolecular Helices: The Role of Intermolecular Interactions in Aggregation

“…Following this line, Díaz-Cabrera et al [21] studied the self-assembly of achiral and chiral 1,3,5-triphenylbenzenetricarboxamides. In a similar way, Greciano et al [22] analyzed the self-assembly of N-annulated perylene bisimides [PBIs], showing the important role of long-range van der Waals and dipoledipole electrostatic interactions in the aggregation mechanism of compounds that lack H-bonding groups.…”

Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes

“…It facilitates the incorporation of intermolecular hydrogen bonds between the neighboring monomers, and thereby induces electronic cooperativity during the supramolecular polymerization process [13][14][15][16][17]. By adopting this principle, a variety of π-conjugated moieties such as arenes, oligo(phenylene ethynylene)s (OPEs), perylene bisimides (PBIs), porphyrins have been reported to form cooperative supramolecular polymers [18][19][20][21][22][23][24][25][26][27][28][29][30].…”