Malononitrile-involved Michael addition polymerization: An efficient and facile route for cyano-rich polyesters with programmable thermal and mechanical properties

An efficient, atom-economic, oxygen-tolerant, and water-tolerant strategy has been established to synthesize cyano-rich polyesters. Four kinds of organic bases, 1,1,3,3-tetramethylguanidine (TMG), 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were explored for accelerating Michael addition polymerization of malononitrile and 1,4-butandiol diacrylate. TMG can promote the polymerization efficiently under mild conditions to quantitatively afford polyester with high-molecular weight and moderate polydispersity. The comparison of the kinetic studies of TMG and TBD reveals that TMG shows better catalytic performance, while the catalysis of TBD brings about oligomers in spite of the higher efficiency at early age of the polymerization. Moreover, other diacrylate compounds could also be quantitatively polymerized to afford polyesters with high molecular weight. When dimethacrylate is chose as the monomer, the polymerization becomes sluggish. All the afforded polyesters display programmable thermal and mechanical properties that are closely related to their chemical structures.     

Thermosetting resins from a tetra-functional vinylbenzene compound possessing cyclic siloxane cores

Cyclic siloxane is an attractive building block for incorporation of silicon-containing units as well as their distinguished properties to polymer materials. This work reports the synthesis and characterization of a tetra-functional vinylbenzene compound possessing cyclic siloxane cores (cD₄-4VB). Synthesis of cD₄-4VB is carried out using cD₄-4SiH as the reactive precursor and multiple-step reactions, including hydrosilylation, deacetylation, and S_N2 substitution. cD₄-4VB is an effective monomer for preparation of the corresponding cyclic silicon-based thermosetting resins (CR-cD₄-4VB). CR-cD₄-4VB shows attractive film formability and good thermo-mechanical properties, including a storage modulus of 2.0 GPa, a glass transition temperature of 282°C, a thermal stability above 400°C, a high char yield (at 800°C in nitrogen) of 55 wt%, and a dielectric constant of 3.12 at 10 GHz. This kind of resins have potential of application for halogen-free flame retardants and high-performance polymer films.     

A Carbocationic Triarylmethane-Based Porous Covalent Organic Network

A thermally stable carbocationic covalent organic network (CON), named RIO-70 was prepared from pararosaniline hydrochloride, an inexpensive dye, and triformylphloroglucinol in solvothermal conditions. This nanoporous organic material has shown a specific surface area of 990 m² g⁻¹ and pore size of 10.3 Å. The material has CO₂ uptake of 2.14 mmol g⁻¹ (0.5 bar), 2.7 mmol g⁻¹ (1 bar), and 6.8 mmol g⁻¹ (20 bar), the latter corresponding to 3 CO₂ molecules adsorbed per pore per sheet. It is shown to be a semiconductor, with electrical conductivity (σ) of 3.17×10⁻⁷ S cm⁻¹, which increases to 5.26×10⁻⁴ S cm⁻¹ upon exposure to I₂ vapor. DFT calculations using periodic conditions support the findings.     

Nanocomposite Hydrogel of Pd@ZIF-8 and Laponite®: Size-Selective Hydrogenation Catalyst under Mild Conditions

The composite hydrogel of a nanoscale metal–organic framework (NMOF) and nanoclay has emerged as a new soft-material with advanced properties and applications. Herein, we report a facile synthesis of a hydrogel nanocomposite by charge-assisted self-assembly of Pd@ZIF-8 nanoparticles with Laponite^® nanoclay which coat the surface of Pd@ZIF-8 nanoparticles. Such surface coating significantly enhanced the thermal stability of the ZIF-8 compared to the pristine framework. Further, the Pd@ZIF-8+LP hydrogel nanocomposite shows better size-selective catalytic hydrogenation of olefins than Pd@ZIF-8 nanoparticles based on selective diffusion of the substrate.     

Isomers of B←N-Fused Dibenzo-azaacenes: How B←N Affects Opto-electronic Properties and Device Behaviors?

The B←N unit has a large dipole and it is isoelectronic to C−C moiety with no dipole. Incorporating B←N units into π-conjugated system is a powerful strategy to design organic small molecules and polymers with intriguing opto-electronic properties and excellent opto-electronic device performance. However, it is unclear how the B←N unit affects electronic structures and opto-electronic properties of large π-conjugated molecules. In this work, to address this question, we developed three dibenzo-azaacene molecules in which two B←N units were introduced at different positions. Although the dibenzo-azaacene skeleton is fully π-conjugated, the effect of B←N unit on the electronic structures of the adjacent rings is much stronger than that of the distant rings. As a result, the three molecules with isomerized B←N incorporation patterns possess different electronic structures and exhibit tunable opto-electronic properties. Among the three molecules, the centrosymmetrical molecule exhibits higher LUMO/HOMO energy levels than those of the two axisymmetrical molecules. When used as the active layer in organic field-effect transistors (OFETs), while the two axisymmetrical molecules show unipolar electron transporting property, the centrosymmetrical molecule exhibits ambipolar hole and electron transporting behavior. This work not only deepens our understanding on organoboron π-conjugated molecules, but also indicates a new strategy to tune opto-electronic properties of organic semiconductors for excellent device performance.     

The Prospect of Dimensionality in Porous Semiconductors

With the advent of silicon-based semiconductors, a plethora of previously unknown technologies became possible. The development of lightweight low-dimensional organic semiconductors followed soon after. However, the efficient charge/electron transfers enabled by the non-porous 3D structure of silicon is rather challenging to be realized by their (metal-)organic counterparts. Nevertheless, the demand for lighter, more efficient semiconductors is steadily increasing resulting in a growing interest in (metal-)organic semiconductors. These novel materials are faced with a variety of challenges originating from their chemical design, their packing and crystallinity. Although the effect of molecular design is quite well understood, the influence of dimensionality and the associated change in properties (porosity, packing, conjugation) is still an uncharted area in (metal-)organic semiconductors, yet highly important for their practical utilization. In this Minireview, an overview on the design and synthesis of porous semiconductors, with a particular emphasis on organic semiconductors, is presented and the influence of dimensionality is discussed.     

露天煤矿排土场地表的光谱特征和土壤参数分析

以辽宁海州煤矿露天排土场为研究对象,分析了地表土壤光谱特征以及反射光谱与地表土壤参数的相关性。土壤反射光谱分析结果表明：不同排土年限光谱反射率随排土年限的增长而降低;不同土质中灰土和混合土的水分吸收谷表征不明显,红壤土、黄土和红砂土光谱反射率以红壤土为最高, 以下依次为黄土和红砂土。土壤反射光谱与土壤参数相关性分析结果表明：有机质含量与反射光谱相关性最高处的相关系数为-0.76,其他参数与反射光谱相关系数较低。建立土壤有机质含量预测模型(建模R2_C=0.737 4,模型检验R2_V=0.682 4)满足检测要求。分析了1 910和1 943 nm处光谱反射率与土壤含水量之间的关系,结果表明由于排土场土壤的多样性和复杂性,土壤全样本光谱反射率与土壤含水量之间呈非线性相关,分别依年代、土质分组后,土壤光谱反射率与土壤含水量均呈线性相关。     

CO2活化温度对碳气凝胶结构及氢吸附性能影响

以间苯二酚(R)和甲醛(F)为前驱体制备出RF碳气凝胶,并利用CO2气体对其进行活化,通过热重分析(TG)、X射线衍射(XRD)、氢吸附等表征手段研究了活化过程中温度对碳气凝胶微结构及氢吸附性能的影响。结果表明：CO2活化可使碳气凝胶比表面积大幅提高,且不会影响其微孔网络结构。随着活化温度的升高,碳气凝胶非晶性变得更加明显,失重率显著增加,微孔体积、比表面积及氢吸附量先增后减,有望通过改变CO2活化温度增加碳气凝胶微孔数量来提高其氢吸附性能。     

Efficient organic photovoltaic cells based on thiazolothiazole and benzodithiophene copolymers with π‐conjugated bridges

New donor–π–acceptor (D–π–A) type conjugated copolymers, poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(4‐octylthiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐tTz), and poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(6‐octylthieno[3,2‐b]thiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐ttTz) were synthesized and characterized with the aim of investigating their potential applicability to organic photovoltaic active materials. While copolymer PBDT‐tTz showed a zigzagged non‐linear structure by thiophene π‐bridges, PBDT‐ttTz had a linear molecular structure with thieno[3,2‐b]thiophene π‐bridges. The optical, electrochemical, morphological, and photovoltaic properties of PBDT‐tTz and PBDT‐ttTz were systematically investigated. Furthermore, bulk heterojunction photovoltaic devices were fabricated by using the synthesized polymers as p‐type donors and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester as an n‐type acceptor. PBDT‐ttTz showed a high power conversion efficiency (PCE) of 5.21% as a result of the extended conjugation arising from the thienothiophene π‐bridges and enhanced molecular ordering in the film state, while PBDT‐tTz showed a relatively lower PCE of 2.92% under AM 1.5 G illumination (100 mW/cm²). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1978–1988