Modular synthesis of polymers containing 2,5‐di(thiophenyl)‐N‐arylpyrrole

A modular and facile route has been developed to synthesize functionalized 2,5‐di(thiophen‐2‐yl)‐1‐H‐arylpyrroles from readily available starting materials. These units are compatible with various polymerization conditions and are versatile building blocks for conjugated polymers. The polymers show high thermal stability and solubility in a number of solvents. Characterization of the polymers reveals a correlation between molecular packing, controllable by polymer design, and charge carrier mobility. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1133–1139     

Highly sensitive H2S sensors based on ultrathin organic single-crystal microplate transistors

Based on ultrathin dinaphtho[3,4-d:3′,4′-d′]benzo[1,2-b:4,5-b′]dithiophene (Ph5T2) single-crystal microplates, the highly sensitive organic field-effect H₂S sensors are realized at room temperature. The response is as high as 1.2 × 10⁶% in 50 ppm H₂S. This value is extremely high for H₂S sensors, and is three orders of magnitude higher than that of the most reported semiconductor gas sensors. The response/recovery time is respectively as low as 2 min and 1 min in 50 ppm H₂S. The detect limitation is as low as 0.5 ppm. The ultrathin single-crystal microplates provide direct and efficient ways for the analytes' activities within the conducting channel, and therefore mainly account for the improved sensing performance. The excellent sensing performance of ultrathin Ph5T2 single-crystal microplate transistors reveals the capacity of developing highly sensitive room-temperature sensors.     

Micro‐/Nanostructured Multicomponent Molecular Materials: Design,Assembly, and Functionality

Molecule‐based micro‐/nanomaterials have attracted considerable attention because their properties can vary greatly from the corresponding macro‐sized bulk systems. Recently, the construction of multicomponent molecular solids based on crystal engineering principles has emerged as a promising alternative way to develop micro‐/nanomaterials. Unlike single‐component materials, the resulting multicomponent systems offer the advantages of tunable composition, and adjustable molecular arrangement, and intermolecular interactions within their solid states. The study of these materials also supplies insight into how the crystal structure, molecular components, and micro‐/nanoscale effects can influence the performance of molecular materials. In this review, we describe recent advances and current directions in the assembly and applications of crystalline multicomponent micro‐/nanostructures. Firstly, the design strategies for multicomponent systems based on molecular recognition and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low‐dimensional multicomponent micro‐/nanostructures. Their new applications are also outlined. Finally, we briefly discuss perspectives for the further development of these molecular crystalline micro‐/nanomaterials.     

Systematic optimization of low bandgap polymer/[6,6]-phenyl C70 butyric acid methyl ester blend photodiode via structural engineering

Synthetic approaches for optimizing polymer-based organic photodiodes (OPDs) by systematically analyzing the effects of the hole-blocking layer, the electron-blocking layer, and the thickness and morphology of the active layer with respect to the dark current and detectivity have been reported. PBDTT-DPP with a repeating alkylthienylbenzodithiophene (BDTT) and diketopyrrolopyrrole (DPP) units is used as a p-type polymer for achieving both broadband absorption and a high absorption coefficient in conjunction with n-type [6,6]-phenyl C₇₀ butyric acid methyl ester (PC₇₀BM) for constructing photoactive layers. Through systematic investigations of various interfacial layers, we found that the thickness of the active layer and the energy level of the hole/electron blocking layer were critical for minimizing the dark current of OPDs. By changing the deposition method of the PBDTT-DPP/PC₇₀BM blend and using post treatment, we discovered that the morphology of the active layer was directly related to the photocurrent of OPDs. Furthermore, we conducted a comparative study between a bulk heterojunction and a planar heterojunction (PHJ) to demonstrate the effectiveness of the PHJ for suppressing the dark current. Consequently, we realized a high detectivity of 5.3 × 10¹² Jones with an optimized device architecture and morphology. This work shows the importance of a synthetic approach for optimizing OPDs that requires both a high photocurrent and a low dark current in the reverse saturation regime.     

On the reliability of determination of energies of HOMO and LUMO levels in organic semiconductors from electrochemical measurements. A simple picture based on the electrostatic model

Relations between energies of ionized levels (HOMO and LUMO levels) obtained from photoelectron spectroscopy (UPS and IPES) of molecular solids, and oxidation (reduction) potentials of respective molecules dissolved in non-aqueous solvents are re-examined. Several classes of molecules are taken into account: polycyclic aromatic hydrocarbons, fullerenes, aromatic amines and anhydrides, sulfur- and selenium-containing molecules, coordination complexes, etc. It is demonstrated that the equations, commonly employed to evaluate the solid state energies of ionized levels from electrochemical measurements, should be modified. Based on literature data gathered for over 100 molecules, empirical correlations are determined allowing for estimation of the solid-state ionization energies and electron affinities from electrochemical experiments. The correlation coefficients depend on the selection of molecules involved and potential range but for the most common combination of these two parameters the following correlations are proposed: I_c = (1.15 ± 0.09) × (eπ_ox) + (4.79 ± 0.07) eV, and A_c = (1.18 ± 0.05) × (eπ_red) + (4.83 ± 0.10) eV. A model is put forward explaining the course of the correlations.     

Solid-State 17O NMR studies of organic and biological molecules: Recent advances and future directions

This Trends article highlights the recent advances published between 2012 and 2015 in solid-state ¹⁷O NMR for organic and biological molecules. New developments in the following areas are described: (1) new oxygen-containing functional groups, (2) metal organic frameworks, (3) pharmaceuticals, (4) probing molecular motion in organic solids, (5) dynamic nuclear polarization, and (6) paramagnetic coordination compounds. For each of these areas, the author offers his personal views on important problems to be solved and possible future directions.     

Enhancing light-extraction efficiency of OLEDs with high- and low-refractive-index organic–inorganic hybrid materials

High- and low-refractive-index hybrid materials were prepared by an in situ acid-free sol–gel process for internal and external light-extraction layers in organic light-emitting diodes (OLEDs). A random copolymer of methyl methacrylate (MMA) and 3-(trimethoxysilyl) propyl methacrylate (MSMA), poly(MMA-co-MSMA), which was capped with trialkoxysilane in MSMA units, was used as a precursor. The precursor was further reacted with titanium(IV) isopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) to synthesize the high- and low-refractive-index hybrid materials, respectively, in which TiO₂ and SiO₂ nanoparticles were well dispersed, respectively, in the polymer matrix. After the reactions with TTIP and TEOS, the refractive index increased to 1.81 and decreased to 1.44 from 1.50 of the precursor, respectively. The luminance, power, and current efficiency of the OLED with an external light-extraction layer were enhanced by 21.3, 28.6, and 29.1%, respectively, those of the OLED with an internal light-extraction layer were increased by 62.4, 76.9, and 59.2%, respectively, and those of the device with combined ELEL and ILEL were enhanced by 62.7, 77.2, and 59.3%, respectively, when compared to values for the reference OLED without an internal or external light-extraction layer. These results indicate that high- and low-refractive-index materials are desirable for enhancement in light-extraction efficiency, and they can provide practical solutions for various applications such as OLED displays and lighting.     

Air‐Stable Spirofluorene‐Containing Ladder‐Type Bis(alkynyl)borane Compounds with Readily Tunable Full Color Emission Properties

A series of air‐stable spiro‐fused ladder‐type boron(III) compounds has been designed, synthesized, and the electrochemistry and photophysical behavior have been characterized. By simply varying the substituents on the pyridine ring and extending the π‐conjugation of the spiro framework, the emission color of these compounds can be easily fine‐tuned spanning the visible spectrum from blue to red. All compounds exhibit a broad and structureless emission band across the entire visible region, assigned as an intramolecular charge‐transfer transition originating from the thiophene of the spiro framework to the pyridine‐borane moieties. In addition, these compounds demonstrate high photoluminescence quantum yields of up to 0.81 in dichloromethane solution and 0.86 in doped thin films. Some of the compounds have also been employed as emissive materials, in which solution‐processed organic light‐emitting devices (OLEDs) with tunable emission colors spanning the visible spectrum from blue, green to red have been realized, demonstrating the potential applications of these boron compounds in OLEDs.     

Annealing-free Poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester-based organic solar cells

We report on the fabrication of efficient annealing-free organic solar cells using co-solvent solution considered as a promising method for low-cost and time-saving manufacturing. Higher device efficiency could be obtained compared to the pure solvent casted device, resulting from the improved crystallinity, optical absorption and transport properties. The power conversion efficiency of 2.8% was obtained, demonstrating the feasibility of achieving low-cost and high-efficiency organic solar cells without any additional treatment and processing additives.     

Lithium perchlorate-diethyl ether as a medium in organic addition reactions. An ersatz to high pressure methodology?

Abstract

The effect of lithium perchlorate-diethyl ether solutions (LPDE) is compared to the pressure effect in several addition reactions. The results cannot be accounted for either internal pressure, or electrostriction, but point to a Lewis-acid catalytic effect, in agreement with recent propositions. It is also concluded that the high pressure methodology is generally superior to the use of LPDE to improve yields.