Impact of Chirality on Hydrogen‐Bonded Supramolecular Assemblies and Photoconductivity of Diketopyrrolopyrrole Derivatives

Abstract

Hydrogen bonds can efficiently guide the self-assembly of organic materials, enabling to tune the properties of the aggregation processes. In the case of p-conjugated materials, several parameters such as temperature, concentration and solvent can be used to modify the aggregation state while tuning the optoelectronic properties. Chirality can be included within the impacting parameters due to the differences in molecular packing. Here, chiral and achiral thiophene-capped diketopyrrolopyrrole derivatives were designed and synthesized containing amide bonds, with the aim to study the interplay between chiral assemblies and their stabilization throughh ydrogen-bonding. Differences in aggregation properties were observed with spectroscopy and microscopy,a nd ac ontactless microwave-based technique was used to study their intrinsic chargec arrierm obility.T he positive role of hydrogen-bonding has been highlighted and the differences between chiral and achiral compoundsh ave been elucidated.

Ultrathin Two Dimensional (2D) Supramolecular Assembly and Anisotropic Conductivity of an Amphiphilic Naphthalene-Diimide

“…Local-scale photoconductivity of the ordered assembly of cNDI-1 was studied by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) technique, ,,− focusing on the charge transport along the stacked cNDI-1 arrays with eliminating the contact resistance and minimizing the effect of the domain sizes and/or impurities. The dropcast films of cNDI-1 on a quartz substrate recorded absorption spectra (Figure S9) similar to those in solution (Figure a), indicating the presence of stacked chromophores.…”

Imaging deposition-dependent supramolecular chiral organisation

“…The relative arrangement of chromophores in a chiral sense will affect the material's photoinduced charge transport, and recent interest in these kinds of systems mean our findings and approach may be of use. [35][36][37]…”

“…The relative arrangement of chromophores in a chiral sense will affect the material's photoinduced charge transport, and recent interest in these kinds of systems mean our findings and approach may be of use. [35][36][37] Fig. 5 Absorption (A), CD (B) and g-factor (C) spectra of 1 in annealed drop-coated film from MMP mapping (green) and spin coated from MMP (black), and from CDi of an as-formed film at 20 1C (red) and annealed at 120 1C (blue).…”

Straightforward N-alkylation of diketopyrrolopyrroles through the Mitsunobu reaction with benzyl, α-branched, and chiral alcohols

“…17 The N-alkyl groups on DPP derivatives play a crucial role not only in the improvement of the solubility but, depending on their nature, they can also affect the structural, conformational, and solid-state organization through intra-and intermolecular interactions with strong consequences on the electronic and photophysical properties. [18][19][20][21][22] For instance, the - stacking interactions (which often determine a quenching of the photoluminescence in the solid state for DPP-based fluorophores) can be considerably reduced by using sterically demanding side chains such as benzyl groups [23][24][25] or -branched alkyl groups. 19,26 This latter class of N-alkyl substituents should be regarded as a practical expedient for introducing stereogenic centres close to the DPP core, opening the way towards a cutting-edge class of chiral fluorophores with enhanced chiroptical properties.…”