Discrete π‐Stacks from Self‐Assembled Perylenediimide Analogues

Abstract

The formation of well-defined finite-sized aggregates represents an attractive goal in supramolecular chemistry. In particular,construction of discrete p-stacked dye assemblies remains achallenge.Reported here is the design and synthesis of an ovel type of discrete p-stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss-cross PEP-PBP dimers in solution and (PBP-PEP)-(PEP-PBP)t etramers in the solid state are well elucidated using single-crystal X-ray diffraction, dynamic light scattering, and diffusion-ordered NMR spectroscopy. Extensive p-p stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow-tailed alkyls ubstituents are responsible for the selective formation of discrete dimer and tetramer stacks.Our results reveal anew approach to preparing discrete p stacks that are appealing for making assemblies with well-defined optoelectronic properties.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

π-Extended perylene diimide double-heterohelicenes as ambipolar organic semiconductors for broadband circularly polarized light detection

“…AFM and XRD analyses both revealed almost no preferred orientation of 3a molecules in thin films. Unlike strong intermolecular orientation of PDI semiconductors using π-π stacking [38][39][40][41][42] , 3a thin films exhibited completely circular or spherical grains, not rod type ones, which indicates their weak intermolecular interactions in the aggregated states, related to loosely, isotropic molecular packing.…”

Understanding intermolecular interactions of large systems in ground state and excited state by using density functional based tight binding methods

“…Here, we considered two cases of large systems. The first is a π-stacked aggregate tetramer composed of an ortho-ethynylene-bridged PDI dyad (PEP) and the slightly longer orthobutadiyne-bridged PDI dyad (PBP), 61 denoted as PBP-PEP-PEP-PBP. This tetramer contains 324 atoms.…”

“…The seven dimer interactions in L7 include: a - stacked interaction in the parallel coronene dimer (C2C2PD), a - stacked interaction in the circumcoronene•••adenine dimer (C3A), a - stacked interaction between circumcoronene and a guanine-cytosine base pair dimer (C3GC), a stacked interaction between two octadecanes (CBH), a - stacked interaction between guaninecytosine base pair dimers (GCGC), a stacked interaction between a single guanine and a guanine dimer (GGG), and an interaction between a single phenylalanine residue and a phenylalanine dimer (PHE). Two model molecules, a π-stacked aggregate tetramer 61 (Figure 1), and an amyloid-like IYQYGG segment 62 (PDB code: 6G8C, Figure 2), were employed to examine the capabilities of DFTB-EDA for large systems. A series of complexes in the ground state and the lowest excited states, shown in Figure 3, were used to examine the application of DFTB-EDA in the excited state.…”

“…The geometries of all complexes shown in Figures S1, S2, 1 and 2 were taken directly from the literature. [59][60][61][62] The complexes in Figure 3 S2. The errors in total interaction energies calculated by DFTB and KS-DFT, compared to those obtained by CCSD(T)/CBS are shown in Table S3.…”

Symmetry-Induced Orderly Assembly Achieving High-Performance Perylene Diimide-Based Nonfullerene Organic Solar Cells

“…To this end, one effective strategy is to design PDI acceptors with controllable self-assembly properties. 13,14 The assembly of aromatic-fused π-conjugated molecules is a powerful tool to calibrate and enhance their optoelectronic properties for applications in OSCs, organic field-effect transistors (OFETs), and organic light-emitting diodes (OLEDs). Understanding the preferred molecular assembly is a requisite for constructing a predictive guideline for developing novel materials with exaggerated performance.…”