Synthesis and properties of polyfluorene copolymers bearing thiophene and porphyrin

To search for more wider absorption and higher charge carriers mobilities materials of polymer solar cell, a series of soluble alternating polyfluorene copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. Their structures were determined by 1H NMR, IR and UV-vis. And their UV-vis absorption spectra indicated that they had strong absorption over 600 nm spectral range and nearly cover 400-700 nm visible region. The band gaps of copolymers calculated according to cyclic voltammetry （CV） were between 1.96 and 2.03 eV. Polymer：TiO2 bulk-heterojunction films were made from mixtures of polymer and titanium isopropoxide, a precursor for TiO2, via hydrolysis in air overnight. The photoluminescence at 380-800 nm of the blend film of PT-TPP20 （5 mg/mL）：Ti（OC3H7）4 （80 μL/mL） （20% volume fraction） was significantly quenched in the 50% Ti（OC3H7）4 blend film, indicating that rapid and efficient separation of photoinduced electron-hole pairs.

Theoretical Investigation on the Luminescent Properties of Polyfluorene and Poly(fluorene-co-thiophene)

The density functional theory was employed to study the structures, ionization potentials（IPs）, electron affinities（EAs）, and HOMO-LUMO gaps（ΔH-L） of the oligomers. The time-dependent density functional theory（TD-DFT） and ZINDO were employed to study the lowest excitation energies（Egs） and the absorption and emission spectra of the oligomers of polyfluorene（PF） and poly（fluorene-co-thiophene）（PFT）. By extrapolating ΔH-L and Egs to those of infinite chain length, band gaps and effective conjugation lengths of the corresponding polymers were obtained. The IPs, EAs and 2abs of the polymers were obtained by extrapolating those of the oligomers to the inverse chain length equal to zero（I/n=0）. The outcome shows the decreased dihedral angle between fluorene and thiophene units in the PFT compared to that between fluorene units in the PF results in the increased efficient conjugation of PFT. These cause both the maximal absorption and emission wavelengths of PFT red-shifted compared with those of PF.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL FLUORINE-CONTAINING HYDROPHOBICALLY ASSOCIATING POLYMER

In this article, the synthesis and characterization of a novel fluoromonomer and its copolymer with acrylamide is reported. 2-perfluoroamyl-4-hydroxylquinoline 2 was synthesized from ethyl 2, 2-dihydroperfluoroheptanoate in high yields. The monomer 4 was then synthesized from 2 in two steps readily in high yields. Synthesis and characterization of copolymers of acrylamide (AM) and the fluoromonomer were investigated. The composition and intrinsic viscosity of these copolymers were studied. It was found that the rheological properties of aqueous solutions of polyacrylamide were modified significantly when a small proportion of the fluoromonomer 4 was incorporated on investigating the viscosity-concentration profiles, pseudoplasticity of these solutions and the effect of the presence of surfactant. These results could be explained by the hydrophobic association of the fluorocarbon segments in the aqueous solutions of these copolymers.

Synthesis of Polyfluorene-Polytriarylamine Block Copolymer with Emitting Part at Junction Point for Light Emitting Applications

A block copolymer consisting of polyfluorene (PF) and polytriarylamine (PTAA) functionalized with green emitting phenoxazine moiety at the junction point of two blocks was designed and prepared for electroluminescent application. PF homopolymer was synthesized by Suzuki coupling polymerization, and was reacted with brominated phenoxazine. In the presence of the resulting PF functionalized with phenoxazine, C-N coupling polymerization of 4-(4’-bromophenyl)-4’’-butyldiphenylamine was carried out to afford a triblock copolymer, PTAA-phenoxazine-PF-phenoxazine-PTAA (PF-Ph-PTAA). Two types of random copolymers were also synthesized with fluorene and phenoxazine (PF2) by Suzuki coupling polymerization for comparison. All the polymers were soluble in common organic solvents and readily formed thin films by a solution processing. Prepared polymers exhibited similar UV absorption and PL emission in chloroform solutions. In a film state, the existence of phenoxazine unit drastically changed PL spectra. Although the content of phenoxazine unit in PF-Ph-PTAA was relatively high (13 mol%), it showed similar PL spectrum to that of PF2(phenoxazine content, 0.2 mol%) indicating that phenoxazine unit is isolated in single polymer chain nevertheless the high content. EL device based on PF-Ph-PTAA showed green-emission, suggesting that emission sites predominantly located in the vicinity of phenoxazine moiety because of its shallow HOMO level.

The synthesis,characterization and X-ray diffractometry structure of fluorine-containing cyclobis(paraquat-p-phenylene) tetracation

Two novel fluorine-containing cyclophanes 1 and 2 incorporating a 1,4-bismethylfluorophenylene subunits have been synthesized via the template-directed clipping methodology and their structure was characterized by ~1H NMR,^(13)C NMR, MALDI-TOF-MS and elemental analysis.X-ray diffraction analysis of the solid state molecular structure showed that the complex units are linked by non-classical C-H…F hydrogen bonding.

The Inorganic-organic Hybrid Junction with n-ZnO Nanorods/p-polyfluorene Structure Grown with Low-temperature Aqueous Chemical Growth Method

The inorganic-organic hybrid junction was synthesized on ITO glass substrate, which was consisted of an n-type ZnO nanorods （NRs） grown by low-temperature aqueous chemical growth method and a p-type polyfluorene （PF） organic film fabricated by spin-coating. The experimental results indicate that densely and uniformly distributed ZnO nanorods are successfully grown on the PF layer. The thickness of the PF layer plays a dominant role for the current-voltage （I-V） characteristic of the ZnO NRs/PF inorganic-organic hybrid junction device, and a p-n junction with obviously rectifying behavior is achieved with optimal PF layer thickness. The photoluminescence （PL） spectrum covering the broad visible range was obtained from the n-ZnO nanorods/p-polyfluorene （PF） structure, which was originated from the combination of the PF-related blue emission and the ZnO-related deep level emission.

Michael Addition of Nitroalkanes to CF_3CCl_2COCH=CHPh: A Facile Route to Fluorine-containing γ-Nitro Ketones

Nitroalkanes react smoothly with CF_3CCl_2COCH=CHPh via Michael addition in the presence of inorganic bases such as KF/Al2O3 or K2CO3, giving fluorinecontaining γ-nitro ketones in good yields.

Synthesis and Characterization of Fluorine-containing Poly(ether ether ketone)s

Poly（ether ether ketone）s（PEEK） are a class of high performance engineering thermoplastics known for their excellent thermal, mechanical, and electrical properties. This class of advanced materials has currently received considerable attention for potential application in aerospace, electronics, automobile and other high technology fields. However, it is difficult for PEEK to be processed because of their high melting temperature and poor solubility.

Research progress on preparation and purification of fluorine-containing chemicals in lithium-ion batteries

With the development of digital products,electric vehicles and energy storage technology,electronic chemicals play an increasingly prominent role in the field of new energy such as lithium-ion batteries.Electronic chemicals have attracted extensive attention in various fields.Characteristics of high-end electronic chemicals are high purity and low impurity content,which requires a very strict separation and purification process.At present,crystallization is a key technology for their separation and purification of electronic chemicals.In this work,the representative fluorine-containing compounds in cathode and anode materials,separator and electrolyte of lithium-ion batteries are introduced.The latest technologies for the preparation and purification of four kinds of fluorine-containing battery chemicals by crystallization technology are reviewed.In addition,the research prospects and suggestions are put forward for the separation of fluorine-containing battery chemicals.

Polyfluorene-Polytriarylamine Block Copolymer as an Additive for Electroluminescent Devices Based on Polymer Blends

Electroluminescent characteristics were investigated for the blue emitting devices fabricated with the blend systems consisting of hole transporting polytriarylamine (PTAA), electron transporting polyfluorene (PF), and a block copolymer with both segments (PF-b-PTAA) as an active layer in order to elucidate the relationship between the chemical nature and morphology of the active layer, and EL performance. The addition of PF-b-PTAA to PF homopolymer afforded the hole injecting and/or electron blocking ability to increase the efficiency. The addition to PF/PTAA blend keeping the chemical composition constant also improved the performance by controlling the morphology and/or the domain size in phase-separated films.

A CONVENIENT SYNTHESIS OF FLUORINE-CONTAINING QUINOLINES

2-Fluoroalkyl-4-hydroxy-quinolines were easily obtained from the reactions of 2-(F-alkyl)acetates with aromatic amines in the presence of Et_3N,followed by cyclization of the intermediates with PPA.

PBO fibers/fluorine-containing liquid crystal compound modified cyanate ester wave-transparent laminated composites with excellent mechanical and flame retardance properties

Bisphenol A dicyanate ester resins modified by fluorine-containing liquid crystal compound(LCFE)are applied as polymer matrix(LCFE-BADCy),poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers as rein-forcements,and fluorine/adamantane PBO precursor(pre FABPBO)as interfacial compatibilizer to prepare the corresponding PBO fibers/FABPBO/LCFE-BADCy wave-transparent laminated composites.LCFE could improve the order degree of BADCy cured network,in favor of enhancing the wave-transparent perfor-mance,mechanical properties,and intrinsic thermal conductivity.The dielectric constant and dielectric loss of PBO fibers/FABPBO/LCFE-BADCy composites are highly temperature(25–200℃)and frequency(10^(4)–10^(7) Hz and 8.2–12.4 GHz)stable with the value of 2.49 and 0.003 under 10^(6) Hz at 25℃,and the corresponding wave transmission efficiency is 95.0%,higher than that of 92.5%for PBO fibers/BADCy com-posites.The interlamellar shear strength and flexural strength are respectively 50.7 MPa and 682.5 MPa,38.1%and 16.2%higher than those of PBO fibers/BADCy composites.Besides,the volume resistivity,breakdown voltage,heat resistance index,glass transition temperature,flame retardant grade,and ul-timate oxygen index of PBO fibers/FABPBO/LCFE-BADCy composites are respectively 5.3×10^(15)Ωcm,29.75 kV/mm,217.2℃,245.7℃,V-1 grade,and 33.6%,expected to be performed as a new generation of“lightweight/loading/wave-transparent”electromagnetic window materials in advanced military weapons and civil communication base station.

Fluorine-containing drugs approved by the FDA in 2021

Nine new fluorine-containing drugs have been approved by the US Food and Drug Administration(FDA)in 2021,which are presented in this review article.These small molecular drugs feature aromatic fluorine,trifluoromethyl and chlorodifluoro groups.The therapeutic areas of these fluorine-containing drugs include multiple myeloma,lymphoma,HIV,chronic heart failure,chronic myeloid leukemia,(ANCA)-associated vasculitis,migraines,von Hippel-Lindau disease,and non-small cell lung cancer.The brief biological activities and the synthetic methods have been discussed in this review for each of these nine drugs.

Low dielectric constant and highly intrinsic thermal conductivity fluorine-containing epoxy resins with ordered liquid crystal structures

Epoxy resins with a high dielectric constant and low intrinsic thermal conductivity coefficient cannot meet the current application requirements of advanced electronic and electrical equipment.Therefore,novel fluorine-containing liquid crystal epoxy compounds(TFSAEy)with fluorinated groups,biphenyl units,and flexible alkyl chains are first synthesized via amidation and esterification reactions.Then,4,4′-diaminodiphenylmethane(DDM)is used as a curing agent to prepare the corresponding fluorine-containing liquid crystal epoxy resins.The obtained dielectric constant(ε)and dielectric loss(tanδ)values of TFSAEy/DDM at 1 MHz are 2.54 and 0.025,respectively,which are significantly lower than those of conventional epoxy resins(E-51/DDM,3.52 and 0.038).Additionally,the intrinsic thermal conductivity coefficient(λ)of TFSAEy/DDM is 0.36 W/(m⋅K),71.4%higher than that of E-51/DDM(0.21 W/(m⋅K)).Meanwhile,the corresponding elastic modulus,hardness,glass transition temperature,and heat resistance index of TFSAEy/DDM are 5.73 GPa,0.35 GPa,213.5◦C,and 188.7℃,respectively,all superior to those of E-51/DDM(3.68 GPa,0.27 GPa,107.2℃,and 174.8℃),presenting potential application in high-heating electronic component packaging and printed circuit boards.

The action mechanisms and structures designs of F-containing functional materials for high performance oxygen electrocatalysis

Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.

聚芴类电致发光材料

聚芴与其衍生物是一类重要的电致发光聚合物,它们具有较高的光致发光效率,并且易于进行结构修饰,因此受到材料化学家们的高度关注。本文叙述的线索是聚合物结构与其电致发光性能之间的构效关系。通过化学修饰,可以调节材料的前线分子轨道、热和光谱稳定性,进而开发新的发光材料。文中首先简单介绍了聚芴类发光材料的聚合方法,然后按结构将这些聚合物分为两个部分进行介绍:一部分是主链仅含有共轭芴单元的聚合物,它们的化学修饰依赖于芴9位的活性碳原子;另一部分是通过共聚方法得到的主链含有芴和其它基团的聚合物。

新型含苯并噻唑及吡唑啉环的聚烷基芴电致发光材料的合成及性能研究

用苯并噻唑基吡唑啉与芴共聚,制备了两种新型的主链含苯并噻唑及吡唑啉环的聚烷基芴电致发光材料。目标聚合物玻璃化温度(Tg)为210和213℃。该聚合物为发光层的结构为ITO/PEDOT/polymer/BCP/Alq/Mg∶Ag的发光二极管起亮电压分别为和10.7和10V,最大亮度为109和105cd/m2。

新型烷基芴共聚物的合成及电致发光性质

用微波加热法快速合成了两种新型的苯并噻唑基吡唑啉,并与芴共聚,制备了两种新型的主链含苯并噻唑及吡唑啉环的聚烷基芴电致发光材料,通过红外和核磁对其进行了表征。目标聚合物的玻璃化温度(Tg)为143℃和117℃,具有良好的热稳定性。用该聚合物为发光层作的结构为ITO/PEDOT/po ly-m er/BCP/A lq/M g:A g的聚合物发光二极管(PLED)起亮电压分别为和9.8 V和11.5 V,最大亮度分别为107 cd/m2和65 cd/m2。

新型芴类发光共聚物

采用Suzuki偶合方法合成了芴与低带隙单体噻吩 (Th)及其衍生物乙烯基二氧噻吩 (EDT )、4 ,7_二噻吩_2 ,1,3_苯并噻二唑 (DBT )、4 ,7_二噻吩_2 ,1,3_苯并硒二唑(BTSe)的二元无规共聚物 ,实现了聚芴颜色的调节 ,得到了发蓝绿光到黄光 (峰值波长在4 90～ 5 6 0nm之间 )以及饱和红光 (峰值波长在 6 2 8～ 718nm )的聚合物 ,所得到的共聚物的光荧光和电荧光量子效率都比文献中所报道的交替共聚物要高得多 .芴与噻吩共聚物的最大电致发光 (EL)外量子效率为 0 .4 5 % ,芴与EDT共聚物的最大EL外量子效率为1.8% ,芴与DBT共聚物的最大EL外量子效率为 1.4 % ,均比文献中所报道的相应聚合物高得多 .芴与BTSe共聚物的最大EL外量子效率为 0 .5 % ,这是首次报道含BTSe的发光聚合物 .实验中还观察到了由于激子在低带隙单体DBT和BTSe位置的捕获而产生的有效的能量转移 。