具有含氧亚甲基中心桥键的含氟液晶化合物的质谱裂解规律研究

利用气相色谱质谱联用仪(GCMS)对含有侧向氟取代苯并吡喃结构和侧向氟取代萘酚(苯酚)结构的16个中心桥键为含氧亚甲基的醚类液晶化合物进行分析,结果表明此两类化合物的谱图具有明显的特征,化合物具有相似的裂解途径。主要是与醚键相连取代基团β位的氢通过四元环过渡态重排脱去中性分子,得到对应的侧向氟取代酚碎片离子;萘酚(苯酚)醚类化合物当结构中有两个烷氧基取代时,当另一个烷氧基也存在β氢时会再一次通过氢重排反应脱去烯烃,得到特征的侧向氟取代二酚碎片离子。对于苯并吡喃醚类化合物,当吡喃环α位有烷基取代时将通过σ键的断裂引起烷基碳碳键的裂解,脱去烷基自由基得到相应的离子;特殊的,对于苯并吡喃醚类液晶化合物其可以通过吡喃环上的氢重排引起吡喃环开环从而得到对应的离子。通过对此两类含有醚键结构的液晶化合物的质谱分析可为该类液晶化合物的杂质解析与质量监测提供依据,将有助于同类液晶衍生物的识别,同时可为混晶的有效剖析提供参考。     

特性炔类液晶的简便合成

4,4′-二烷基-4-乙炔基联环己烷(1)和它的偶联衍生物1,4-双((4,4′-二烷基-联环己)-4-基)丁二炔(2)、1,4-双(2-((4,4′-二烷基-联环己)-4-基)乙炔基)芳烃(3)是具有某种特性的重要液晶化合物。文章介绍了以4,4′-二烷基联环己基-4-甲腈(4)为起始原料的化合物的合成。首先,化合物(4)与甲基锂发生加成反应,水解后制得关键中间体甲基酮化合物(5),接着甲基酮化合物(5)与格氏试剂在特定的条件下反应,高收率地制得炔类化合物(1),关于本反应可能的机理文中也进行了阐述。化合物(1)通过氧化自偶联制得化合物(2)。化合物(1)与二卤代芳烃在Pd(0)催化系统下发生偶联制得化合物3,这些化合物的制备具有短的合成步骤和高的反应收率,是高效的合成方法;其中化合物(1)的制备方法从未见诸于以前的任何文献报道。     

三氟甲基芳环类液晶的合成新方法

以烷基（环己基）（联）苯为基本原料,经过磺代反应以后,与三所氟乙酸钠反应得到４-烷基（环已基）三氟甲基芳环类液晶化合物。反应收率高、操作简单、成本相对较低。共合成了７个三氟甲基芳环类液晶化合物。所有化合物都经过ＩＲ,１Ｈ—ＮＭＲ,ＭＳ谱图和元素分析检测,确定其分产结构,并经ＤＳＣ测得液晶相态温度范围。     

4-(trans-4-n-烷基环己基甲氧基)-4'-氰基联苯的合成

以ｔｒａｎｓ－４－ｎ－烷基环已基甲醇和４－溴－４’－羟基联苯为原料合成了一组４－（ｔｒａｎｓ－４－ｎ－烷基环已基甲氧基）－４’－氰基联苯类液晶化合物,用ＩＲ、ＭＳ、元素分析确证了化学结构。研究发现铜盐对ｔｒａｎｓ－４－ｎ－烷基环已基甲醇的溴代反应有催化作用;在相转移催化剂的作用下进行醚化获得较高收率;氰代反应以Ｎ－甲基－２吡咯烷酮溶剂效果较好。ＤＳＣ测试结果表明该类液晶化合物具有较高的清亮点。     

4-(3-烯)正丁基-2′氟-4″丙基-[1,1′,4′1″]三联苯的合成

丁烯类液晶具有黏度小、熔点低、清亮点高、低温稳定性良好的优点,对改进混晶的性能有着显著作用,是一类具有广阔前景的液晶单体。本文经过对接、酰化、酯化反应得到2-氟-4-溴-1-乙酸乙酯基联苯,与丙基苯硼酸偶联、还原、氯代得到4-氯甲基-2′-氟-4″丙基-[1,1′,4′1″]三联苯,再与3-氯丙烯的格氏试剂偶联,共7步反应得到目标产物4-(3-烯)正丁基-2′氟-4″丙基-[1,1′,4′1″]三联苯,总收率为21.7%。最后对化合物进行了IR、H1 NMR、GC-MS表征。     

多卤代联苯类化合物及其制备的液晶单体

以2,3,3′,5′-四氟-1,1′-联苯为原料,在超低温条件下与n-BuLi及CF_2Br_2反应得到一种新的多卤代联苯类化合物4′-二氟溴甲基-2,3,3′,5′-四氟-4-溴-1,1′-联苯,利用一步反应同时向分子结构中引入-CF_2Br和-Br两个不同的官能团,简化了反应步骤。用此化合物作为通用中间体,可以方便地合成多种二氟甲醚桥键类液晶单体,为此类液晶单体的制备提供了一种新的方法,文中用上述方法合成了二氟甲醚桥键类液晶单体3PYUQUF,液晶综合参数测试结果表明,化合物3PYUQUF的Δ_n值为0.138 0,Δ_ε值为22.63。     

α-氰基肉桂酸酯类液晶的合成与性质研究

以对羟基苯甲醛和氰基乙酸乙酯缩合生成α-氰基对羟基肉桂酸乙酯,再与4种酰氯反应生成α-氰基肉桂酸酯类液晶;以对羟基苯甲醛和氰基乙酸丙基苯酚酯缩合生成α-氰基对羟基肉桂酸丙基苯酚酯,再与2种烷基环己基甲酰氯反应生成α-氰基肉桂酸酯类液晶.目标化合物经MS分析确认了结构.通过差示扫描量热仪测量相变温度,对合成产物的液晶相态进行了研究;通过紫外分光光度计测量紫外光谱,研究了合成产物紫外吸收性能.在混合液晶中的应用实验表明,此类化合物可以作为具有液晶性能的紫外吸收剂添加到混合液晶中,改善液晶材料的抗紫外性能.     

4-(6-羟基己氧基)联苯-4′-甲酸-L-2甲基丁醇酯的合成及其液晶性的研究

运用示差扫描量热仪、偏光显微镜、X射线衍射仪和计算机模拟分子链处于能量最低、最优构象时的分子长度等手段,对新合成的4-(6-羟基己氧基)联苯-4′-甲酸-L-2甲基丁醇酯进行表征。结果表明:该液晶化合物为近晶A相。合成总收率为47.3%(相对于4-羟基-4′-氰基联苯)。     

液晶材料反-4-[反-4-（4-三氟甲氧基苯基）环己基]环己基-1-乙烯的合成

文章以对三氟甲氧基溴苯和单乙二醇缩4,4＇-双环己基二酮为起始原料,经格氏反应,脱水、氢化、脱保、转型、wittig反应、水解、转型和wittig反应,最终合成了液晶材料反-4-[反-4-（4-三氟甲氧基苯基）环己基]环己基-1-乙烯。其中脱水反应最佳溶剂选二甲苯,反应时间4h;氢化反应选Pd／C作催化剂;纯化后目标产物的纯度为99．5％（GC）,总收率约为27．8％,其结构经IR、^1H NMR及MS确证。     

含氟联苯乙炔类液晶的合成

丁基溴苯和间氟苯硼酸经Suzuki偶联生成4′丁基-3-氟联苯,4′丁基-3-氟联苯在低温下碘代生成3-氟-4-碘-4′-丁基联苯,3-氟-4-碘-4′-丁基联苯与5种取代苯乙炔发生Sonogashira反应生成5种含氟联苯炔类单体液晶。进行了产品结构的标定以及参数的测定,确定了化合物具有较大的光学各向异性(Δn)和较宽的向列相范围。     

2,5,8,11-Tetra-Tertbutylperylene作为辅助掺杂剂的红色有机电致发光二极管(英文)

制备了采用9,10-di-(2-naphthyl)anthracene(ADN)作为主体,4-(dicya-nomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran(DCJTB)作为红色发光中心,2,5,8,11-tetra-tertbutylperylene(TBPe)作为辅助掺杂剂的红光有机电致发光器件。4,4′,4″-tris[2-naphthyl(phenyl)amino]triphenylamine(2TNATA)用作空穴注入材料,4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl(NPB),tris-(8-hydroxyquinoline)aluminum(Alq3)用于空穴和电子传输。实验结果表明,掺有DCJTB的ADN也可实现红色发光,掺入TBPe作为辅助掺杂,可以提高该红光器件的效率,但几乎不改变器件色坐标。此外,2%TBPe(质量分数)作为辅助掺杂的器件表现出最佳的流明效率和最大升温速率。     

Ternary flash memory device based on polycarbazole with ZrO2 composite materials

The poly[2,7-9-(9-heptadecanyl)-9H-carbazole-co-benzo[4,5] imidazole[2,1-a]isoindol-11-one] (PCz-O) was synthesized by Suzuki coupling reaction, which structure was verified by FT-IR, ¹H NMR and ¹³C NMR. The spin coating method was used to prepare RRAM devices based on PCz-O: ZrO₂ nanoparticle active layer, and the devices exhibited ternary switching. Through a series of performance tests, both pure polymer device and composited with ZrO₂ NPs devices had ternary storage characteristics. Among them, the content of composited with 8 wt% ZrO₂ showed the most excellent ternary storage characteristics. The ON/OFF current ratio was 2.60 × 10⁴, and the threshold voltage V_th1/V_th2 was −0.60 V/-1.00 V. The current is stable for 10000 s in both ON/OFF states. After 3300 times of reading, the switch state current of the devices had slight variation. In addition, the switching mechanism of the device was also discussed. Through carefully testing and analyzing, the devices had good stability and durability, and had potential application value in terms of data storage.     

含氟反式环己基联苯液晶的合成

分别以PdCl2或Pd2(dba)3(CHCl3)作催化剂,K3PO4作碱,吡啶为溶剂,通过Suzuki交叉偶联反应合成了3个含氟反式环己基联苯液晶。与PdCl2相比,Pd2(dba)3(CHCl3)催化效力高,用量少(摩尔分数为0.25%),能有效催化多氟-反式环己基联苯类液晶的合成,纯产品产率达80%～67%,该反应体系简单、高效,催化剂合成储存方便,经济实用,具有较高的工业应用前景。     

NiCuZn铁氧体的组成对PZT/NiCuZn材料性能的影响

首先用sol-gel法制得了Pb0.95Sr0.05(Zr0.52Ti0.48)O3纳米粉料(简称PZT),然后采用固相反应法制备了ζ(PZT:NiCuZn)为1:9和3:7的两种复合材料。研究Ni0.26-xCu0.19+xZn0.55Fe2O4铁氧体的组成对低温烧结复合材料的显微结构、电磁性能的影响。结果表明:当x=0.02的化学组成为主配方时,复合材料可实现900℃低温烧结,且ζ(PZT:NiCuZn)为1:9的复合材料的μi高达92,Q值为39,ε′为19;而ζ(PZT:NiCuZn)为3:7的复合材料的μi为26,Q值为19,ε′为32。     

A laser augmented reaction: SF6+ SiH4→S*2+ SiF4+ HF + H2· retention of isotopic selectivity during detonation

A single unfocused pulse of a free running CO2laser, area ∼ 8 cm², initiates an explosive reaction between SF6and SiH4. This occurs at a minimum energy of 4 J [full width at half maximum (FWHM)sim 1.5 /mus] of which about one half is absorbed in an 8 cm long cell; total pressure 12 torr; 0.65 <p(SiH4)/p(SF6) < 1.8. The spectral and temporal distributions of the emitted chemiluminescence depend sensitively on the fuel to oxidizer ratio, and on the pulse energy; we investigated the range 4 → 20 J. The principal emission is due to S2(B^{3}Sigma-_{u} rightarrow X^{3}Sigma-_{g}). Transitionsupsilon' (0-4) rightarrow upsilon" (2-15)were recorded. In the³Sigma-_{u}state, vibrational temperatures range from 3000-13000 K. The luminosity peaks sharply at (SiH4)/(SF6) = 1.0 ± 0.05. On each side of the maximum of the emission versus composition curve [at (SiH4)/(SF6) ≈ 0.95 and 1.22, for a 12 J pulse] the residual SF6(0.2-0.5 percent of initial amount) is enriched in³⁴SF6; the observed fractionation factors at these two compositions are 8 ± 2. The separation between the two sharply peaked optimum compositions appears to increase with increasing pulse energy. Preliminary results with other fuels suggest that the concurrent absorption of CO2laser radiation by the fuel, as well as a highly exothermic reaction, are pre-requisite for fine tuning of composition, injected power, and total pressure for optimum isotope fractionation.     

A wide-bandgap copolymer donor with a 5-methyl-4H-dithieno[3,2-e:2',3'-g]isoindole-4,6(5H)-dione unit

Wide-bandgap copolymer donors with fused-ring accept-or units (FAUs) present excellent performance in non-fullerene organic solar cells due to their complementary light-absorption with nonfullerene acceptors,deep the highest occupied molecular orbital (HOMO) levels and high hole mobilities[1-4].A bunch of FAU-based copolymer donors were developed in recent years,such as PM6[s],PM7[6],PBQx-TCI[7],PTQ10[8],PBQ6[9],P2F-EHp[10],D16[11],L1-S[12],D18[13,14]and D18-CI[1s,16].They delivered ＞16％ power conversion effi-ciencies (PCEs) in solar cells.To develop good FAUs is the key toward efficient FAU-based copolymer donors.A good FAU generally has a strong electron-withdrawing character that leads to a low HOMO level and a high open-circuit voltage(Voc),and a relatively large molecular plane that facilitates poly-mer stacking and enhances hole mobility.Recently,we de-veloped copolymer donors D18 and D18-CI by using dithi-eno[3',2':3,4;2",3":5,6]benzo[1,2-c][1,2,5]thiadiazole (DTBT)unit[13] (Fig.1(a)).Thanks to the strong electron-withdrawing property and the rigid and extended molecular plane of DTBT,D18 and D18-CI deliver outstanding PCEs up to 18.69％[13-16].The success of D18 polymers stimulated us to design more high-performance copolymer donors with nov-el FAUs.In this work,we designed a wide-bandgap copoly-mer donor P1 by using a fused-ring imide building block,5-methyl-4H-dithieno[3,2-e:2',3'-g]isoindole-4,6(5 H)-dione(MDTID).Compared with the thiadiazole moiety in DTBT,the imide moiety in MDTID is more electron-withdrawing.The density functional theory (DFT) calculations show that MDTID has deeper HOMO and the lowest unoccupied molecular orbit-al (LUMO) levels than DTBT,suggesting the stronger electron-accepting capability of MDTID (Fig.1(a)).DFT calculations also indicate that MDTID leads to a deeper HOMO for P1 than that of D18,thus benefiting Voc (Fig.S1).     

Deep blue organic light-emitting diode using non anthracene-type fused-ring spiro[benzotetraphene-fluorene] with aromatic wings

We prepared three spirobenzotetraphene-based fused-ring spiro[benzo[ij]tetraphene-7,9′-fluorene] (SBTF) derivatives for use in non anthracene-type deep-blue organic light-emitting diode (OLED) hosts. 3-(2-Naphthyl)-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (N-NSBTF), 3-[4-(2-naphthyl)phenyl]-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (NP-NSBTF), and 3-(phenyl)-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (P-NSBTF) were synthesized via multi-step Suzuki coupling reactions. The optimized device structure – ITO/N,N′-bis-[4-(di-m-tolylamino)phenyl]-N,N′-diphenylbiphenyl-4,4′-diamine (DNTPD, 60 nm)/bis[N-(1-naphthyl)-N-phenyl]benzidine (NPB, 30 nm)/NSBTF hosts: LBD (5%) (20 nm)/aluminum tris(8-hydroxyquinoline) (Alq₃, 20 nm)/LiF/Al – was characterized by its blue electroluminescence to have a current efficiency of 6.25 cd/A, a power efficiency of 5.07 lm/W, and an external quantum efficiency of 5.24% at 18.7 mA/cm² at CIE coordinates of 0.130, 0.149.     

对称性分子间氢键诱导液晶

本文以４－［（４－烷氧基苯甲酰氧基）－４’－苯乙烯基］－吡啶（７ＳＺ和１０ＳＺ）为质子受体．以脂肪族二元羧酸（ｍＤＡ）为质子给体，合成了对称性的氢键复和物。其液晶行为经ＤＳＣ和偏光显微镜研究，结果表明复合物的液晶范围较相应的质子受体的液晶范围宽．     

Columnar Liquid Crystals with a Central Crown Ether Unit

Novel columnar liquid crystals 5a – f bearing a dibenzo[18]crown[6] central unit have been prepared from bromodialkyloxybenzenes 1 and tetrabromodibenzo[18]crown[6] 2 via Suzuki coupling reactions. Differential scanning calorimetry (DSC) revealed that the length of the alkyl chains in the liquid‐crystalline compounds 5 influenced their mesomorphic properties. Whereas 5a – d gave fan‐shaped textures only upon rapid cooling, 5e and 5f with C9 and C10 side chains formed stable columnar textures upon slow cooling. A hexagonal columnar mesophase of 5a is apparent from X‐ray diffraction studies. Complexation of 5 with potassium significantly shifted the clearing points to higher temperatures and also increased the mesophase stability in the cooling cycle.