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Fluorine-phenanthroimidazole Porous Organic Polymer: Efficient Microwave Synthesis and Photocatalytic Activity
摘要： A porous polymer containing a fluorophenylphenanthroimidazole core was easily prepared via one-pot Suzuki-Miyaura cross coupling reactions under microwave heating. These new metal-free polymers have demonstrated heterogeneous photocatalytic activity toward aza-Henry reaction with reasonable recyclability. Their preparation require a minimal workup to build porous networks with control over the apparent surface area and pore volume from suitable molecular building blocks containing the 2-(1H-phenanthro[9,10-d]imidazol-2-yl)-3,5-difluorophenol (PhIm-2F), as rigid and multitopic node which afforded a conjugated porous polymer (CPP-PhIm-2F). A series of fluorinated ligands have shown their capability to preparation of soluble and supported cationic Ru(bpy)2(F-phenanthroimidazole)-complexes by reaction with Ru(bpy)2Cl2 and demonstrated a beneficial effect of two fluorine atom on the photocatalytic effect.
关键词： Conjugated polymer,Ruthenium photocatalyst,Photocatalysis,Aza-Henry,Heterogenized catalyst,Porous organic polymer,Phenanthroimidazole
更新于2025-09-23 15:19:57
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Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties
摘要： The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV–visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems.
关键词： fluorination,conjugated block-copolymer synthesis,microphase stabilization,polythiophene,temperature-dependent Raman spectroscopy
更新于2025-09-19 17:15:36
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Conducting Polymers || Electrical Properties of Polymer Light-Emitting Devices
摘要： In this chapter, we present a brief introduction to semiconducting properties of conjugated polymers and the motivation to apply this class of materials in electronic/optoelectronic devices such as polymer light-emitting diodes (PLEDs). We describe, in detail, the operating mechanisms of PLEDs, with particular focus on the effects of charge injection and transport and their dependence on the external electric field and temperature. The mechanisms of current injection from the electrodes into the organic semiconductor are initially treated using traditional models for thermionic emission and tunnelling injection. More recent models considering the influence of metal/semiconductor interface recombination and of energetic and spatial disorder in the injection currents are also introduced and discussed. In addition, models considering space-charge-limited currents and trap-filling-limited currents are employed to describe the charge transport characteristics in the bulk. Furthermore, we present a brief discussion on ideas concerning the effects of the disorder on the charge-carrier transport behaviour.
关键词： space-charge-limited currents,conjugated polymers,polymer light-emitting diodes,organic semiconductors,electrical properties
更新于2025-09-19 17:15:36
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Ferrocene Linkage Facilitated Charge Separation in Conjugated Microporous Polymers
摘要： Conjugated microporous polymers (CMPs) have full access to the organic synthesis toolbox and feature-rich functionality, structural diversity, and high surface area. We incorporated ferrocene (Fc) into the backbones of CMPs and systematically engineered their optical energy gaps. Compared with the CMPs without Fc units yet adopting similar molecular orbital level, Fc-based CMPs can sufficiently generate reactive oxygen species (ROS) under visible light. The resultant ROS are able to effectively decompose the absorbed pollutants, including organic dyes and chemical warfare agents. Specifically, Fc-based CMPs significantly outperform commercial TiO2 (P25) in the degradation of methylene blue and are capable of converting 2-chloroethyl ethyl sulfide (a mustard gas simulant) into completely nontoxic product.
关键词： conjugated microporous polymer,charge separation,photocatalytic degradation,ferrocene,reactive oxygen species
更新于2025-09-19 17:15:36
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Metal Free Acid-Mediated Solid-State Polymerization and Processability of Polymers Based on 3,4-Alkylenedioxythiophenes
摘要： The present article reports metal free acid-mediated polymerization of 3,4-alkylenedioxythiophenes in a solvent free medium and processability of insoluble polymers. It also describes structural variants and functional aqueous dispersions based on 3,4-alkylenedioxythiophenes. Polymers were processed by dispersing the insoluble polymer powders in aqueous media using polymeric aromatic surfactant (polystyrenesulfonate, PSS) and aliphatic surfactant (sodiumdodecylsulfonate, SDS), respectively. The effect of surfactant on particle size, stability, and conductivity of the dispersions was investigated in detail. Polymer particles in SDS-based dispersions tend to agglomerate which resulted enhanced conductivity of the thin films. Electrochemical studies revealed that the polymers are electroactive in nature and are transparent in oxidized state. The electrochromic contrast between the oxidized and reduced states of the polymers was in the range of 40–46%.
关键词： ProDOT,aqueous dispersion,3,4-ethylenedioxythiophene,PEDOT:PSS,conjugated polymers
更新于2025-09-19 17:15:36
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Conjugated HCl-doped polyaniline for photocatalytic oxidative coupling of amines under visible light
摘要： HCl-Doped polyaniline (PANI-ES) and PANIs of different oxidation states were prepared by a typical oxidative polymerization and subsequent redox reaction, respectively. The photocatalytic performance of PANIs towards selective benzylamine oxidation reactions under visible light was investigated. PANI-ES containing a polaron structure exhibited the highest light-induced activity (54.9%). The results show that the formation of the surface complex between PANI-ES and adsorbed amine should be responsible for the enhanced visible light activity. The newly formed polaron band in PANI-ES has a greater number of delocalized electrons, which can facilitate electron transfer and thus improve the photoactivity. These results indicate that conjugated conducting polymers can be efficient visible light-responsive nonmetal photocatalysts for green synthesis.
关键词： Conjugated polyaniline,Amines,Visible light,Oxidative coupling,Photocatalysis
更新于2025-09-19 17:15:36
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Direct Observation of Structure and Dynamics of Photogenerated Charge Carriers in Poly(3-hexylthiophene) Films by Femtosecond Time-Resolved Near-IR Inverse Raman Spectroscopy
摘要： The initial charge separation process of conjugated polymers is one of the key factors for understanding their conductivity. The structure of photogenerated transients in conjugated polymers can be observed by resonance Raman spectroscopy in the near-IR region because they exhibit characteristic low-energy transitions. Here, we investigate the structure and dynamics of photogenerated transients in a regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend film, as well as in a pristine P3HT film, using femtosecond time-resolved resonance inverse Raman spectroscopy in the near-IR region. The transient inverse Raman spectrum of the pristine P3HT film at 50 ps suggests coexistence of neutral and charged excitations, whereas that of the P3HT:PCBM blend film at 50 ps suggests formation of positive polarons with a different structure from those in an FeCl3-doped P3HT film. Time-resolved near-IR inverse Raman spectra of the blend film clearly show the absence of charge separation between P3HT and PCBM within the instrument response time of our spectrometer, while they indicate two independent pathways of the polaron formation with time constants of 0.3 and 10 ps.
关键词： polaron,femtosecond inverse Raman spectroscopy,conjugated polymer,bulk heterojunction
更新于2025-09-19 17:15:36
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Surface-Controlled Crystal Alignment of Naphthyl End-Capped Oligothiophene on Graphene: Thin-Film Growth Studied by <i>In Situ</i> X-ray Diffraction
摘要： We report on the microstructure, morphology, and growth of 5,5′-bis(naphth-2-yl)-2,2′-bithiophene (NaT2) thin films deposited on graphene, characterized by grazing-incidence X-ray diffraction (GIXRD) and complemented by atomic force microscopy (AFM) measurements. NaT2 is deposited on two types of graphene surfaces: custom-made samples where CVD-grown graphene layers are transferred onto a Si/SiO2 substrate by us and common commercially transferred CVD graphene on Si/SiO2. Pristine Si/SiO2 substrates are used as a reference. The NaT2 crystal structure and orientation depend strongly on the underlying surface, with the molecules predominantly lying-down on the graphene surface (face-on orientation) and standing nearly out-of-plane (edge-on orientation) on the Si/SiO2 reference surface. Post growth GIXRD and AFM measurements reveal that the crystalline structure and grain morphology differ depending on whether there is polymer residue left on the graphene surface. In situ GIXRD measurements show that the thickness dependence of the intensity of the (111) reflection from the crystalline edge-on phase does not intersect zero at the beginning of the deposition process, suggesting that an initial wetting layer, corresponding to 1-2 molecular layers, is formed at the surface-film interface. By contrast, the (111) reflection intensity from the crystalline face-on phase grows at a constant rate as a function of film thickness during the entire deposition.
关键词： surface-controlled alignment,molecular orientation,conjugated oligomers,GIXRD,small π-conjugated molecules,two-dimensional materials
更新于2025-09-19 17:13:59
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Organic-inorganic hybrid composites as an electron injection layer in highly efficient inverted green-emitting polymer LEDs
摘要： Organic-inorganic hybrid light emitting diodes (HyLEDs) consist of an organic emission layer in combination with at least one metal oxide charge injection layer in an inverted structure. Low temperature, solution processing of metal oxide charge injection layers is one of the key factors in reducing the manufacture cost of HyLEDs. Herein, we report the use of composite materials, comprising conjugated polyelectrolytes (CPE) and zinc oxide nanoparticles (ZnO NPs), as the electron injection layer (EIL) in highly-efficient, green-light-emitting poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) polymer LEDs that are carefully optimised for use in an inverted HyLED architecture for the first time. The composite CPE:ZnO EILs are processed via a room temperature, one-step, solution deposition and enable superior device performance relative to ZnO NPs on their own. We find that specifically, they (i) improve EIL morphology, reducing surface roughness as well as pin-hole size and density, (ii) induce a favourable vacuum level shift for electron injection by coordinate bonding between the CPE and ZnO constituents, and (iii) reduce interfacial quenching by passivation of ZnO chemical defects caused by oxygen vacancies. This work is also the first demonstration that blending ZnO NPs and CPE supports much faster electroluminescence turn-on times (~7.12 μs) than for traditional ZnO/CPE bilayer devices (~0.4 s) via ‘locking’ of the CPE mobile ions, as well as higher device performance. This demonstrates good suitability for display applications. After optimisation of the EIL composition and the thickness of the F8BT emissive layer, we achieve promising device efficiencies of 16.5 cd/A and 5.41 lm/W for devices with a 1.1 μm thick F8BT layer, which is particularly relevant for potential roll-to-roll fabrication. These results clearly demonstrate the potential that this organic-inorganic composite EIL material has for the realisation of cheap, scalable and highly efficient, printable HyLED devices.
关键词： inverted,Hybrid light-emitting diodes,nanoparticles,electron injection layers,conjugated polyelectrolytes,zinc oxide
更新于2025-09-19 17:13:59
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Photocontrolled synthesis of na??type conjugated polymers
摘要： Current approaches to synthesize π-conjugated polymers (CPs) are dominated by thermally driven, transition metal-mediated reactions. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces all-conjugated n-type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor-acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n-type CPs without the need for transition metal catalysis.
关键词： photopolymerization,transition-metal-free,conjugated polymer
更新于2025-09-19 17:13:59