Despite great challenges, the development of new molecular structures with multiple and even conflicting characteristics are eagerly pursued for exploring advanced applications. To develop high-performance chiral organic semiconducting molecules, a distorted π-system is required for strong coupling with circularly polarized light (CPL), whereas planar π-stacking systems are necessary for high charge-carrier mobility. To address this dilemma, in this work, we introduce a skeleton merging approach through distortion of a perylene diimide (PDI) core with four fused heteroaromatics to form an ortho-π-extended PDI double-[7]heterohelicene. PDI double helicene inherits a high dissymmetry factor from the helicene skeleton, and the extended π-planar system concurrently maintains a high level of charge transport properties. In addition, ortho-π-extension of the PDI skeleton brings about near-infrared (NIR) light absorption and ambipolar charge transport abilities, endowing the corresponding organic phototransistors with high photoresponsivity of 450 and 120 mA W−1 in p- and n-type modes respectively, along with a high external quantum efficiency (89%) under NIR light irradiations. Remarkably, these multiple characteristics enable high-performance broadband CPL detections up to NIR spectral region with chiral organic semiconductors.
An efficient method using N-substituted side chain engineering is demonstrated for tuning the supramolecular chirality and optoelectronics of perylene diimides.
Chiral self-sorting has great potential for constructing new complex structures and determining chirality-dependent properties in multicomponent mixtures. However, it is still of great challenge to achieve high fidelity chiral self-discrimination. Besides, the researches on the coordination polymers or metal−organic frameworks for micro/nanooptoelectronics are still rare due to their low conductivity and difficulty in developing a rapid and simple scale-up synthetic method. Here, heterochiral supramolecular coordination networks (SCNs) were synthesized by the solvothermal reaction of naphthalene diimide enantiomers and cadmium iodide, using the chirality as a synthetic tuning parameter to control the morphologies. Intriguingly, heterochiral micro/nanocrystals exhibited photochromic and photodetecting properties. Furthermore, we also developed a simple and efficient doping method to enhance the conductivity and photoresponsivity of micro/nanocrystals using hydrazine. From experimental and theoretical studies, the mechanism was suggested as follows: the radicals in the singly occupied molecular orbital level of the ligands provide charge carriers that can undergo "through-space" transport between π−π stacked ligands and the electron transfer from adsorbed hydrazine to the SCNs results in reduction of energy gap, leading to increased conductivity. Our findings demonstrate a simple and powerful strategy for implementing coordination networks with redox ligands for micro/nanooptoelectronic applications.
Ambipolar polymeric semiconductors based on a diketopyrrolopyrrole backbone that can be solution-processed using non-chlorinated solvents are reported.
Supramolecular chirality has attracted a great deal of attention as a platform for both fundamental study and chirality amplification in various research fields. Compared with the “sergeants‐and‐soldiers” principle, the “majority‐rules” principle, which affects chirality amplification in supramolecular systems, is rarely reported for nano/microstructures. Here, chiral tetrachloro‐substituted perylene diimides are synthesized that self‐assemble into chiral supramolecules with different degrees of enantiomeric excess (ee). Interestingly, it is found that quasi‐2D crystals are gradually transferred to 1D nanowires (NWs) with ee from 100% to 0%. In the racemic system, chiral self‐discrimination is observed due to the greater thermodynamic stability of heterochiral crystals than the homochiral counterparts, judging from the theoretical studies. Circular dichroism analysis indicates that the self‐assembled system with different ee values shows different peaks due to their unique molecular ordering for supramolecular exciton coupling. On measurement in optoelectronic devices, racemic 1D NWs show better charge transport ability than enantiomeric quasi‐2D crystals. These results provide guidelines for tuning the supramolecular chirality and optoelectronic performance of self‐assembled systems via the “majority‐rules” principle.
Halide perovskites are expected to be widely used in light-emitting diodes (LEDs) due to their excellent optoelectronic properties, such as high luminous efficiency, controllability of luminescence wavelength, and wide color gamut. However, because the exciton binding energy of 3D halide perovskite films is relatively low (%150 meV), various techniques have been applied to increase the exciton binding energy and thereby improve the performance of devices. Among them, 0D halide perovskite nanocrystals (NCs) are widely used because the low-dimensional perovskite effectively confines the excitons in NCs. In particular, perovskite NCs facilitate color tuning with quantum confinement by controlling the size. Herein, it is aimed to provide an overview of various approaches for synthesizing perovskite NCs and post-treatment methods to achieve high-efficiency LEDs.
Two n-type pyridine and selenophene-containing polymers were synthesized and the structure–property relationships were investigated, followed by polarity switching from ambipolarity to unipolar characteristics via the doping method.
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