Cyano-Substituted Perylene Diimides with Linearly Correlated LUMO Levels

A series of nonbay region cyano-substituted tetrachloro­perylene diimides with tunable LUMO energy levels from −4.21 to −4.64 eV were developed. The excellent linear correlation between LUMO energy levels and the number of cyano groups indicated that the LUMO energy levels could be lowered effectively and predictably by incorporating cyano groups

Cyano-Substituted Perylene Diimides with Linearly Correlated LUMO Levels

A series of nonbay region cyano-substituted tetrachloro­perylene diimides with tunable LUMO energy levels from −4.21 to −4.64 eV were developed. The excellent linear correlation between LUMO energy levels and the number of cyano groups indicated that the LUMO energy levels could be lowered effectively and predictably by incorporating cyano groups

Cyano-Substituted Perylene Diimides with Linearly Correlated LUMO Levels

A series of nonbay region cyano-substituted tetrachloro­perylene diimides with tunable LUMO energy levels from −4.21 to −4.64 eV were developed. The excellent linear correlation between LUMO energy levels and the number of cyano groups indicated that the LUMO energy levels could be lowered effectively and predictably by incorporating cyano groups

Cyano-Substituted Perylene Diimides with Linearly Correlated LUMO Levels

A series of nonbay region cyano-substituted tetrachloro­perylene diimides with tunable LUMO energy levels from −4.21 to −4.64 eV were developed. The excellent linear correlation between LUMO energy levels and the number of cyano groups indicated that the LUMO energy levels could be lowered effectively and predictably by incorporating cyano groups

Soluble Twisted Diarenoperylenes: Synthesis, Characterization, and Device Performance

Two stable TIPS-ethynyl functionalized polycyclic aromatic hydrocarbons (PAHs), dibenzo­[<i>a</i>,<i>j</i>]­perylene (<b>TIPS-DBP</b>), and dinaphtho­[<i>a</i>,<i>j</i>]­perylene (<b>TIPS-DNP</b>), which contain two rows of linear acenes joined by benzene rings, have been synthesized and characterized. It is found that the two twisted PAHs easily form one-dimensional charge-transport systems with short C–C contacts. The crystal of <b>TIPS-DBP</b> shows a hole mobility up to 0.17 cm² V^–1s^–1, while the crystal of <b>TIPS-DNP</b> shows a hole mobility up to 0.74 cm² V^–1 s^–1

Palladium-Catalyzed Si–C Bond Formation toward Sila-Annulated Perylene Diimides

The first example of sila-annulation onto the perylene diimide core that allows the effective and practical synthesis of both sila- and disilaperylene diimides (Si-PDIs and 2Si-PDIs) in one pot through palladium-catalyzed Si–C bond formation is presented. The corresponding sila-annulated perylene diimides demonstrated exceptional optical properties with noteworthy bathochromic shifts and excellent fluorescence quantum yields. Single crystal analysis revealed almost planar molecular structures and distinct packing arrangements with intense π–π interactions. Their single crystal OFET devices showed good electron mobilities of up to 0.3 cm² V^–1 s^–1 under a nitrogen atmosphere

Thermally Sensitive Self-Assembly of Glucose-Functionalized Tetrachloro-Perylene Bisimides: From Twisted Ribbons to Microplates

Chiral supramolecular structures are becoming increasingly attractive for their specific molecular arrangements, exceptional properties, and promising applications in chiral sensing and separation. However, constructing responsive chiral supramolecular structures remains a great challenge. Here, glucose-functionalized tetrachloro-perylene bisimides (GTPBIs) with thermally sensitive self-assembly behaviors are designed and synthesized. In a methanol/water mixture, GTPBIs self-assembled into twisted ribbons and microplates at 4 and 25 °C, respectively. Furthermore, the ribbon structure was metastable and could transform into microplates when the temperature was increased from 4 to 25 °C. Transmission electron microscopy (TEM) was used to track the evolution of morphology and study the assembly mechanisms of correponding nanostructures at different time intervals. The supramolecular structures were characterized with various techniques, including circular dichroism, TEM, scanning electron microscopy, atomic force microscopy, ultraviolet–visible absorption, and fluorescence spectra. This study provides insight into controlling molecular parameters and assembly conditions to construct chiral supramolecular structures

Laterally Expanded Rylene Diimides with Uniform Branched Side Chains for Solution-Processed Air Stable n‑Channel Thin Film Transistors

Molecular packing motifs in solid states is the dominant factor affecting the n-channel organic field-effect transistors (OFETs). However, few systematic researches were performed in the different extensions of π-conjugated molecules with the uniform substitution effecting the molecular packing motifs. In this manuscript, OFET devices based on three latterally expanded rylene diimides end-functionalized with uniform 3-hexylundecyl substitution on the imide positions were systematically studied on the relationship of molecular stacking, film microstructure, and charge transport. As the π-conjugated systems expanded from doubly linked perylene diimide dimer (d-4CldiPDI, <b>1</b>), triply linked perylene diimide dimer (t-4CldiPDI, <b>2</b>), to hybrid array (NDI-PDI-NDI, <b>3</b>), their corresponding molecular packing motifs exhibited a divide: the optimized molecular configuration became more planar and <i>d</i> (001) spacing distances became larger, which resulted in a larger π–π overlapping. Thus, an enhanced electron mobility was obtained. A typical n-channel field-effect characteristic was observed in thin film devices based on these molecules under ambient conditions. Especially, the hybrid system (<b>3</b>) with more planar and π-expanded aromatic backbone exhibited superior electron mobility approaching 0.44 cm² V^–1 s^–1 and on/off ratio of 10⁶ after optimal annealing in this study

Nonfused Electron Acceptors Based on the 2D-Extended Quinoxaline Core for Organic Solar Cells

Nonfused electron acceptors have recently attracted considerable attention, primarily owing to their inherent merits, which encompass straightforward synthetic methodologies, heightened yield efficiencies, and economic viability. In this study, we have undertaken the deliberate design and synthesis of two distinct nonfused electron acceptors, denoted as BTIC-4F and PTIC-4F, featuring a two-dimensional (2D) extended electron-deficient quinoxaline moiety as the central core and a 4H-cyclopenta[1,2-b:5,4-b′]dithiophene (CPDT) bridge that connects the cores to the terminal groups. The crystallinity and packing behaviors of acceptors have been finely tuned through the strategic manipulation of diverse two-dimensional extended central nuclei. Subsequently, PTIC-4F with a phenanthrene-fused quinoxaline core exhibits enhanced crystallinity and a more organized molecular packing structure. Therefore, this structural optimization translates into a remarkable outcome, with the PBDB-T:PTIC-4F-based device achieving a substantially elevated power conversion efficiency of 11.24% compared to that of its PBDB-T:BTIC-4F counterpart. The findings of our study underscore the promise inherent in extending electron-deficient core units as a viable and fruitful avenue for the design of nonfused electron acceptors

Effect of Fluorination on Molecular Orientation of Conjugated Polymers in High Performance Field-Effect Transistors

Fluorinated conjugated polymers have been widely used in high performance polymer solar cells, but they showed limited application in field-effect transistors (FETs). In this paper, we focus on the influence of fluorine atoms upon charge transport of conjugated polymers in FET devices. Two series of conjugated polymers without or with fluorine atoms were designed and applied into FETs. Nonfluorinated conjugated polymers show high hole mobilties up to 11.16 cm² V^–1 s^–1, while fluorinated polymers exhibit low hole mobilities below 1.80 cm² V^–1 s^–1. Further investigation by differential scanning calorimetry (DSC) and 2D grazing-incidence wide-angle X-ray scattering (2D-GIWAXS) reveal that fluorinated conjugated polymers show low crystallinity and “face-on” orientation in thin films, explaining their poor hole mobilities in FET devices. Our results clearly show how the chemical structures influence the charge transport properties, which can be used to design new conjugated polymers toward high performance FETs