Chiral self-sorted multifunctional supramolecular biocoordination polymers and their applications in sensors

Chiral supramolecules have great potential for use in chiral recognition, sensing, and catalysis. Particularly, chiral supramolecular biocoordination polymers (SBCPs) provide a versatile platform for characterizing biorelated processes such as chirality transcription. Here, we selectively synthesize homochiral and heterochiral SBCPs, composed of chiral naphthalene diimide ligands and Zn ions, from enantiomeric and mixed R-ligands and S-ligands, respectively. Notably, we find that the chiral self-sorted SBCPs exhibit multifunctional properties, including photochromic, photoluminescent, photoconductive, and chemiresistive characteristics, thus can be used for various sensors. Specifically, these materials can be used for detecting hazardous amine materials due to the electron transfer from the amine to the SBCP surface and for enantioselectively sensing a chiral species naproxen due to the different binding energies with regard to their chirality. These results provide guidelines for the synthesis of chiral SBCPs and demonstrate their versatility and feasibility for use in various sensors covering photoactive, chemiresistive, and chiral sensors

Ab initio powder analysis of kinetically trapped metastable sulfur in a porous network

2

Selective encapsulation of meta-stable sulfur by porous coordination network

2

Effects of microwave-assisted annealing on the morphology and electrical performance of semiconducting polymer thin films

Organic field-effect transistors (OFETs) based on p-channel polymer semiconductors such as poly(3-hexyl)thiophene (P3HT) and 30-diketopyrrolopyrrole-selenophene vinylene selenophene (30-DPP-SVS) were fabricated using a microwave (MW) irradiation process for thermal annealing. The influence of MW annealing was investigated based on microstructural characterizations such as X-ray diffraction (XRD) and atomic force microscopy (AFM). MW annealing not only shortened the annealing time, but also produced enhanced device performance including higher on/off ratio, lower threshold voltage, and higher field-effect mobility in comparison with the traditional annealing method. These microstructural analyses revealed that annealing by MW irradiation enhances the crystallinity and molecular orientation in the polymer thin films in a short time, thereby improving the electrical performance effectively. Our results suggest that MW-assisted annealing is a simple and viable method for enhancing OFET performance.close

Selective Trapping of Labile S₃ in a Porous Coordination Network and the Direct X‑ray Observation

S₃ is one of the basic allotropes of sulfur but is still a mysterious labile species. We selectively trapped S₃ in a pore of a thermally stable coordination network and determined S₃ structure by <i>ab initio</i> X-ray powder diffraction analysis. S₃ in a pore has a <i>C</i>_2<i>v</i> bent structure. The network containing trapped S₃ is remarkably stable under ambient conditions and is inert to photoirradiation. S₃ in the network could be transformed to S₆ by mechanical grinding or heating in the presence of NH₄X (X = Cl or Br). S₆ could be reverse-transformed to S₃ by photoirradiation. We also determined the structure of the network containing S₆ by <i>ab initio</i> X-ray powder diffraction analysis

Selective Trapping of Labile S₃ in a Porous Coordination Network and the Direct X‑ray Observation

S₃ is one of the basic allotropes of sulfur but is still a mysterious labile species. We selectively trapped S₃ in a pore of a thermally stable coordination network and determined S₃ structure by <i>ab initio</i> X-ray powder diffraction analysis. S₃ in a pore has a <i>C</i>_2<i>v</i> bent structure. The network containing trapped S₃ is remarkably stable under ambient conditions and is inert to photoirradiation. S₃ in the network could be transformed to S₆ by mechanical grinding or heating in the presence of NH₄X (X = Cl or Br). S₆ could be reverse-transformed to S₃ by photoirradiation. We also determined the structure of the network containing S₆ by <i>ab initio</i> X-ray powder diffraction analysis

Surface Doping Effect on the Optoelectronic Properties of Tetrachloro-Substituted Chiral Perylene Diimide Supramolecular Nanowires

In nature, chirality displays itself in diverse forms and on various hierarchical scales. Among the various types of chirality, supramolecular chirality is of particular interest due to its ability to amplify and induce chirality, which aids in understanding the fundamental principles of chirality transfer and is also suitable for chirality applications at the macroscopic scale. Herein, we report the synthesis of a novel chiral organic semiconductor 2,9-di(hexan-2-yl)anthra[2,1,9-def:6,5,10-d&apos;e&apos;f&apos;]diisoquinoline-1,3,8,10 (2H, 9H)-tetraone (ClCPDI-C6) and its selfassembly into supramolecular nanowires (NWs). The chirality of the NWs was successfully transferred via intra- and inter-molecular interactions from the chiral pendant to the perylene diimide (PDI) core after self-assembly. Upon exposing the organic NWs to phenylhydrazine dopant vapor, the average mobility of the NW transistor was increased from 0.0085 to 0.026 cm2 V-1 s-1. Additionally, phenylhydrazine molecular doping of the NWs significantly enhanced their optical performance in comparison with the undoped NWs, with improved photoresponsivity (R) (similar to 3 times higher), photosensitivity (P) (similar to 10 times higher), external quantum efficiency (similar to 3 times higher), and detectivity (D*) (similar to 8 times higher). The detectivity of the phenylhydrazine-doped NWs was 1 or 2 orders of magnitude higher than that previously reported for chiral PDI NWs. Notably, they showed a fast and stable real-time photoswitching of both undoped and doped ClCPDI-C6 NWs (&lt;90 ms), indicating a high sensitivity to visible light and great potential in photodetector and photoswitching applications. From density functional theory calculations, after absorbing phenylhydrazine on the ClCPDI-C6 NWs, the increased electron affinity contributes to increased optoelectronic performance. Our investigation paves the way for future in-depth studies on the relationship between the structure and supramolecular chirality with optoelectronic device performance

Bay-Substitution Effect of Perylene Diimides on Supramolecular Chirality and Optoelectronic Properties of Their Self-Assembled Nanostructures

One-dimensional (1D) organic chiral supramolecules have received a great deal of attention for their promising applications in chiral recognition systems, chemical sensors, catalysts, and optoelectronics. Compared to modifications at the imide position of a perylene diimide (PDI), few studies have explored bay substitution of chiral PDIs and their self-assemblies into 1D nanomaterials. Herein, we describe the synthesis of three bay-substituted PDIs and explore the effects of bay substitution on supramolecular chirality by examining circular dichroism spectra and the optoelectronic performance of chiral PDI nanomaterials in phototransistors. Among the three fabricated self-assemblies, nanomaterials based on (R)-CN-CPDI-Ph exhibited the highest electron mobility of 0.17 cm(2) V-1 s(-1), a low threshold voltage of -1 V, and enhanced optoelectronic performance. For example, the photoresponsivity and external quantum efficiency of (R)-CN-CPDI-Ph assemblies were 4-fold higher than those of (R)-2Br-CPDI-Ph and (R)-2F-CPDI-Ph. All three nanomaterials exhibited fast switching speeds compared with previously reported N-substituted PDIs, suggesting that bay substitution can be an effective means of achieving rapid photoswitching. A comprehensive study using density functional theory calculations and crystal analyses revealed that the enhanced optoelectronic performance of (R)-CN-CPDI-Ph nanomaterials is related to the substitution of CN at the bay position of PDI. This minor change provides simultaneous improvements in electron injectability and structural order. Our findings demonstrate that bay substitution can significantly impact the self-assembly, supramolecular chirality, and optoelectronic properties of PDI nanomaterials