Organic solar cells based on chlorine functionalized benzo[1,2-b:4,5-b′]difuran-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione copolymer with efficiency exceeding 13%

Benzo[1,2-b:4,5-b′]dithiophene(BDT) has been widely used to construct donor-acceptor(D-A) copolymers in organic solar cells(OSCs). However, benzo[1,2-b:4,5-b′]difuran(BDF), an analogue of BDT, has received less attention than BDT. The photovoltaic performance of BDF copolymers has lagged behind that of BDT copolymers. Here, we designed and synthesized two BDF copolymers, PBF1-C and PBF1-C-2Cl. PBF1-C-2Cl, which is composed of BDF and benzo[1,2-c:4,5-c′]dithiophene-4,8-dione connected by a chlorinated thiophene π-bridge, displays a low-lying highest occupied molecular orbital energy level,which helps in yielding a high open-circuit voltage(V_(oc)) in OSCs. As a result, when blended with Y6, PBF1-C-2Cl-based devices showed a high V_(oc) of 0.83 V and a power conversion efficiency(PCE) of 13.10%. To the best of our knowledge, the PCE of 13.10% is among the highest efficiency values for OSCs based on BDF copolymers.     

2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves

2D conductive metal–organic frameworks (2D c-MOFs) feature promising applications as chemiresistive sensors, electrode materials, electrocatalysts, and electronic devices. However, exploration of the spin-polarized transport in this emerging materials and development of the relevant spintronics have not yet been implemented. In this work, layer-by-layer assembly was applied to fabricate highly crystalline and oriented thin films of a 2D c-MOF, Cu₃(HHTP)₂, (HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene), with tunable thicknesses on the La_0.67Sr_0.33MnO₃ (LSMO) ferromagnetic electrode. The magnetoresistance (MR) of the LSMO/Cu₃(HHTP)₂/Co organic spin valves (OSVs) reaches up to 25 % at 10 K. The MR can be retained with good film thickness adaptability varied from 30 to 100 nm and also at high temperatures (up to 200 K). This work demonstrates the first potential applications of 2D c-MOFs in spintronics.     

Organic synthesis--art or science?

The LHASA rules for finding strategic bonds in polycyclic target structures are analyzed with respect to the following question: Do the strategic bonds tend to give the greatest simplification upon disconnection, as measured by recently introduced indices of molecular complexity? The answer is yes, at least for the more general rules. This result implies that the bonds most useful for retrosynthetic disconnection can now be identified by a simple calculation rather than by application of a body of rules. It is concluded that organic synthesis, as far as described by these rules, has a mathematical basis and consequently can be considered a science as well as an art.     

Palladium-Catalyzed C-H Bond Functionalization of Benzo[1,2-b : 4,5-b′]dithiophene-4,8-dione: A One Step Access to 2-Arylbenzo[1,2-b : 4,5-b′]dithiophene-4,8-diones

The reactivity of benzo[1,2-b : 4,5-b′]dithiophene-4,8-dione in Pd-catalyzed C−H arylation was investigated. Using aryl bromides as aryl source in the presence of carbonate bases in 1,4-dioxane, the mono-C2-arylated benzo[1,2-b : 4,5-b′]dithiophene-4,8-diones were regioselectively obtained. This procedure allowed to introduce both electron-rich and electron-poor aryl substituents on the benzo[1,2-b : 4,5-b′]dithiophene-4,8-dione unit. These conditions were also effective for the coupling with 1-bromonaphthalene, 9-bromophenanthrene as well as aryl bromides bearing synthetically useful nitrile, chloro and methoxy substituents. The photophysical properties of representative arylated compounds have been performed by joint experimental and theoretical studies.     

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three-dimensional cubane-1,4-dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB-30), comprising cdc, 4,4′-biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.     

Organic/inorganic nanocomposite polymer electrolyte

The organic/inorganic nanocomposites polymer electrolytes were designed and synthesized. The organic/inorganic nanocom-posites membrane materials and their lithium salt complexes have been found thermally stable below 200℃. The conductivity of the organic/inorganic nanocomposites polymer electrolytes prepared at room temperature was at magnitude range of 10-6 S/cm.     

Organic Photovoltaic Properties Based on Oligothiophenes

Organic photovoltaic devices have attracted a great attention because of their light weight and processability, and the ease of material design on the molecular level. There are a number of reports on organic photovoltaic devices using a variety of dyes1-…     

Acceleration of Organic Reactions Using Microwave

The use of microwave technology in accelerating organic reactions has received intense attention leading to immense growth recently. Accordingly, we have been interested in improving the efficacy of organic processes by microwave irradiation. Here we report our results on the microwave assisted direct amide formation from carboxylic acid and amine, the hydrolysis of biopolymers, and nucleophilic aromatic substitution reaction. The reactions carried out under microwave irradiation, in general, …     

Organic–inorganic hybrid melting gels

Melting gels are a class of organically modified silica gels that are rigid at room temperature, flow at temperature T1 and consolidate at temperature T2 (T2 > T1), when crosslinking is complete. The process of (a) softening, (b) becoming rigid and (c) re-softening can be repeated many times. Mixtures of mono-substituted alkoxysilanes and di-substituted alkoxysilanes have been studied in a systematic way to identify suitable melting gel compositions. The mixtures and the resulting melting gels have been characterized for their softening temperatures and consolidation temperatures. With an interest in using these materials for sealing microelectronics, their physical properties have been measured.     

"Handbook of Organic Chemistry"

本书由Dean,J.A.编著,由McGraw—Hill在1987年出版。它以表格形式按英文字母顺序给出了4000种有机化合物及与有机化学相关的无机化合物的名称、结构式、分子量、Beilstein文献、密度、折光指数、熔点、沸点、闪点和溶解度。其中一部分还给出了物理性质(包括粘度、介电常数、偶极矩和表面张力)、     

Synthesis of substituted 4-hydroxy-1H-thieno[2,3-b;4,5-b′]dipyridin-2-ones

Substituted 4-hydroxy-1H-thieno[2,3-b;4,5-b′]dipyridin-2-ones were prepared by the reactions of 3-cyanopyridine-2(1H)-thiones with alkyl 4-chloroacetoacetates and by intramolecular cyclization of alkyl 4-(2-pyridylthio)acetoacetates or alkyl 3-(3-aminothieno[2,3-b]pyridin-2-yl)-3-oxopropionates under the action of bases.     

White and Red Organic Light Emitting Materials

Derivatives of 2,3-(1,4-dialkoxyaceno)norbornadiene underwent ring-opening metathesis polymerization (ROMP) upon the catalysis of a ruthenium complex to afford the corresponding polymers. The polymeric materials containing anthracene chromophores emit white electro-luminescence, which can be fabricated into light-emitting diodes (LED). The broad emission band is composed of a blue emission from anthracene and a red emission from aggregates. A single layer device, ITO/polymer/Ca/Al, can be…     

Small Organic Molecules for Direct Aldol Reaction

Since the pioneering finding by List and Barbas III and their coworkers that L-proline could work as a catalyst in the intermolecular direct aldol reaction, the concept of small organic molecules as catalysts has received great attention. However, new organic molecule which have better catalysis ability are reported scarcely. Our groups1 found L-Prolinamides 1 to be active catalysts for the direct aldol reaction of 4-nitrobenaldehyde with neat acetone at room temperature. The enantioselecti…     

Some Organic Reactions in Supercritical Carbon Dioxide

Organic reactions in supercritical carbon dioxide (scCO2) have facilitated great progress in recent years . ScCO2, as an environmentally friendly reaction medium, may be a substitute for 1 volatile and toxic organic solvents and show some special advantages. Firstly, CO2 is inexpensive, nonflammable, nontoxic and chemical inert under many conditions. Secondly, scCO2 possesses hybrid properties of both liquid and gas, to the advantage of some reactions involving gaseous reagents. Control o…     

Special Issue of ＂Organic Solids＂

The science of organic solids is the interdiscipline across chemistry, physics, photonics, electronics, magnetism, and various other specialties. Its research objects are focusing on exploitation of organic compounds and polymers having specific optical, electronic, and/or magnetic properties and their application technologies in photovoitaics, light-emitting diodes, field-effect transistors, and so on.     

Characterization of A New Organic Photochromic Compound

A new organic photochromic compound, 1-phenyl-3-methyl-4-(4-fluoro)-benzal-5-pyrazolone ethanyl-thiosemicarbazone (PM4FBP-ETSC) was found to undergo photochromic reactions in the solid state. Upon irradiation with 365nm light the white powder sample turned light yellow. The photochromic properties were characterized by the time-dependent UV-vis reflective spectra. The structure of PM4FBP-ETSC was determined by single crystal X-ray diffraction.     

A Near-infrared Non-fullerene Acceptor with Thienopyrrole-expanded Benzo[1,2-b:4,5-b′]dithiophene Core for Polymer Solar Cells

A near-infrared non-fullerene acceptor(NFA) BDTIC, based on thienopyrrole-expanded benzo[1,2-b:4,5-b′]dithiophene unit(heptacyclic S,N-heteroacene) as core, is designed and synthesized. The aromatic pyrrole ring with strong electron-donating ability in the core enhances the intramolecular charge transfer effect, finely tunes the optical bandgap and absorption profile of BDTIC, and thus results in a narrowed optical bandgap(E_g~(opt)) of 1.38 eV and a near-infrared absorption to 900 nm. When BDTIC is paired with donor polymer PBDB-T to fabricate organic solar cells, the optimized device achieves a best power conversion efficiency of 12.1% with a short-circuit current density of 20.0 mA·cm~(-2) and an open-circuit voltage of 0.88 V. The photovoltaic performance benefits from the broad absorption, weak bimolecular recombination, efficient charge separation and collection, and favorable blend morphology. This work demonstrates that thienopyrroleexpanded benzo[1,2-b:4,5-b′]dithiophene unit(heptacyclic S,N-heteroacene) is a promising building unit to construct high-performance NFAs by enhancing the intramolecular charge transfer effect, broadening absorption as well as maintaining good intermolecular stacking property.     

Benzo[1,2-b:4,5-b′]dithiophene-based conjugated polyelectrolyte for the cathode modification of inverted polymer solar cells

A conjugated polyelectrolyte (CPE) named PBNBr, is prepared by post-quaternizing of poly{4,8-bis(octyloxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-9,9-bis(3′-((N,N-dimethylamino)propyl)fluorene-2,7-diyl} (PBN) with bromoethane. The chemical strucutes, electrooptical properties of the PBNBr is fully characterized. As compared with the PBN, the PBNBr exhibit much better methanol solution processibility, and more effectively tuning ability for the work function (W_f) of ITO (W_F bare ITO, ?4.8 eV, W_F of ITO with PBN interlayer, ?4.1 eV, W_F of ITO with PBNBr interlayer ?3.9 eV). The open circuit voltages (V_OC) and power conversion efficiencies (PCEs) of polymer solar cells from the blend film of poly(3-hexylthiophene) (P3HT) and [6,6]-phenylC₆₁-butyric acid methyl ester (PC₆₁BM) with PBN and/or PBNBr modified ITO as cathode are respectively increased about 27% and 120% in contrast to those for the control devices with bare ITO as cathode. And PCEs of 4.21% and 4.53% are achieved in the PSCs with PBN and/or PBNBr modified ITO as cathode.     

A Japan–UK Collaboration in Organic Synthesis

This invited Team Profile was created by Shuo Wang, Igor Larrosa , Hideki Yorimitsu and Greg Perry . They recently published an article on carboxylic acid salts as dual-function reagents for carboxylation and carbon isotope labeling. This project brought together researchers based in Japan and the UK, and demonstrates how scientists with different cultural backgrounds can work together to build powerful results. “Carboxylic Acid Salts as Dual-Function Reagents for Carboxylation and Carbon Isotope Labeling”, S. Wang, I. Larrosa, H. Yorimitsu, G. J. P. Perry, Angew. Chem. Int. Ed. 2023 , e202218371 .