Columnar Packing Motifs of Functionalized Perylene Derivatives: Local Molecular Order Despite Long-Range Disorder

Abstract

We elucidate local packing motifs and dynamical order parameters in a perylene tetracarboxydiimide derivative (C(8,7)-PDI), one of the most promising candidates for rationally designed, self-assembling, and self-healing molecular wires. Spectroscopic fingerprints obtained from solid-state NMR spectroscopy are interpreted by means of first-principles calculations and molecular dynamics simulations. The interplay of steric repulsion, H bonding, and pi-pi packing effects leads to a specific relative molecular pitch angle of approximately 35 +/- 10 degrees between successive molecules in the stack. Dynamical order parameters, determined from NMR sideband patterns as a measure of molecular motion, yield values of S approximately = 1.0 in the core of the columnar stack, corresponding to an almost frozen molecular dynamics at ambient temperature. This rigidity is compatible with characteristic intermolecular distances obtained from dipolar couplings between specific hydrogens via double-quantum NMR experiments and further supported by ab initio calculations.

Mesoscale molecular network formation in amorphous organic materials

“…3D shows that the planar and spherical topologies of PDI and C 60 are inherited in the network topologies as stacks and globules, respectively. The orientational correlation data also demonstrate that electrical connections between PDI derivatives are limited solely to stacked orientations, in agreement with the columnar structures and strong mobility anisotropy experimentally associated with this class of materials (39,40). As we show below, however, the restricted orientational space for establishing connections between PDIs leads to an unexpected fragilizing effect on the mesoscopic electrical networks.…”

N‐Type Self‐Assembled Monolayer Field‐Effect Transistors and Complementary Inverters

“…The π -π stacking of the aromatic cores leads to parallel stacks with a typical distance of 0.36 nm. [23][24][25] where the aromatic chains are arranged perpendicular to the substrate surface. However, the stacks arrange themselves in twisted columns without long range order.…”

“…Due to the difference in mobility, the currents Information Figure S2). The interplay between steric repulsion of branched alkyl tails, π -π packing effects, and self-assembly of the phosphonic acid groups ultimately results in nano-crystalline self-assembled monolayers of PBI-PA. [ 24 ] …”

Kooperative Molekülbewegungen innerhalb eines selbstorganisierten flüssigkristallinen molekularen Drahtes am Beispiel eines TEG‐ substituierten Perylendiimids

“…Fortschritte in der Festkörper-NMR-Spektroskopie [15][16][17] ermöglichen es, Struktur und Dynamik solcher Systeme durch 13 C-NMR-Spektroskopiemethoden in natürlicher Häufigkeit zu untersuchen. Zur Analyse genutzt werden dabei sowohl 13 C-1 H-Dipol-Dipol-Kopplungen (DDC), die das Bewegungsverhalten der C-H-Bindungsrichtung in der Molekül-ebene zeigen, als auch die Anisotropie der chemischen Verschiebung (CSA) der aromatischen 13 C-NMR-Signale, deren Tensorhauptachse senkrecht auf der Molekülebene steht.…”

“…Im Unterschied zu seinem alkylsubstituierten Analogon, [13] [21] durchgeführt (Abbildung 2 b,c). H}-heteronuclearen dipolaren Wiedereinkupplungsexperimenten (REPT-HDOR-und REREDOR-Techniken [21] ) für b) den flüssigkristallinen und c) den eingefrorenen Zustand von TEG-PDI; die Frequenzabhängigkeit der Seitenbandenmuster, angegeben in Vielfachen der Rotationsfrequenz w R , dient zur Bestimmung der dipolaren Kopplungskonstante D und des dynamischen Ordnungsparameters S. Die erhaltenen Muster zeigen, dass die effektiven 13 13 C-CSA-Mustern zu verstehen, muss der Einfluss der axialen Bewegung des Kerns auf die 13 C-CSATensoren und 13 C{ 1 H}-dipolaren Kopplungstensoren betrachtet werden. Abbildung 3 a zeigt die beiden Spektrentypen für den starren Fall.…”