1,4-二[(9-苯基)-9H-3-咔唑基)]苯的合成及其光电性能

以对二溴苯和(9-苯基)-9H-3-咔唑硼酸为原料,通过Suzuki偶联反应合成了一种新型含咔唑磷光主体材料——1,4-二[(9-苯基)-9H-3-咔唑基)]苯(1),其结构经1H NMR,13C NMR和IR表征。UV,荧光光谱和循环伏安法的光电性能研究结果表明,1具有咔唑基团的紫外-可见吸收和荧光特性,与4,4-二(9-咔唑)联苯相比,最低空轨道的能级降低。     

N,N-二[4-(9H-9-咔唑基)苯基]-3,5-二溴苯胺的合成

以3,5-二溴苯胺,碘苯和咔唑为原料,经取代和Ullmann反应合成了一个新的含咔唑三苯胺化合物——N,N-二[4-(9H-9-咔唑基)苯基]-3,5-二溴苯胺,其结构经1H NMR,13C NMR和ESI-MS表征。     

4,5-二苯基-2-(9-苯基-9H-3-咔唑基)-1H-咪唑的合成及其性能

以联苯甲酰、对溴苯甲醛和乙酸铵为原料,经缩合反应制得2-(4-溴苯基)-4,5-二苯基咪唑(1); 1与N-苯基-3-咔唑硼酸经Suzuki偶联反应合成了一种具有D-π-A结构的新型咪唑衍生物4,5-苯基-2-(9-苯基-9H-3-咔唑基)-1H-咪唑(2）,其结构经¹H NMR, ¹³C NMR, IR和MS(EI)表征。采用FL, UV-Vis,循环伏安法（CV）和理论计算对2的光电性能进行了研究。结果表明：2的最大吸收波长为302 nm和326 nm,荧光发射波长为395 nm和412 nm, HOMO和LUMO轨道能级分别为5.35 eV和2.14 eV。     

1-(4-吡啶基)苯基-3,5-二[4-(9’H-9’-咔唑基)苯基]苯的合成及其光学性能

以咔唑、对二溴苯、4-溴苯胺和1,3,5-三溴苯为原料,经重氮化、Ullmann反应、硼酸化和Suzuki等反应合成了一种新型的荧光配体———1-(4-吡啶基)苯基-3,5-二[4-(9’H-9’-咔唑基)苯基]苯(6),其结构经1H NMR,MS和元素分析表征。研究了6在二氯甲烷中的紫外吸收光谱和荧光光谱。结果表明,6在237 nm,293 nm和345 nm处有较强吸收;6的最大发射波长在413 nm。     

新型4-{4,5-二[(E)-苯乙烯]-1H-咪唑-2-基}苯甲醛共价键连单羟基四苯基卟啉化合物的合成及其分子内能量转移性能

以2,3-丁二酮为原料,依次与苯甲醛和对苯二甲醛经缩合反应制得4-{4,5-二[(E)-苯乙烯]-1H-咪唑-2-基)苯甲醛}(2);以对二氯苄作为连接链,2与其经取代反应制得4-{1-[4-(氯甲基)苄基]-4,5-二[(E)-苯乙烯]-1H-咪唑-2-基}苯甲醛(3);3与单羟基四苯基卟啉(4)连接合成了4-{4,5-二[(E)-苯乙烯]-1H-咪唑-2-基}苯甲醛共价键连单羟基四苯基卟啉化合物(5),其中2,3和5为新化合物,其结构经1H NMR,MS和元素分析表征。用荧光光谱研究了5中基团3与基团4之间的能量转移过程。结果表明,当激发取代基团3时,能量能够从基团3转移至基团4上。     

两种新型咔唑衍生物的合成及其光电性能

以咔唑、三苯基氯硅烷及2-溴芴为原料,经甲基化、硼酸化、Ullmann偶联、Suzuki偶联等反应合成了两种新型咔唑衍生物--3,6-二(9,9-二甲基-9H-2-芴基)-9-苯基-9H-咔唑(1a)和3,6-二[(4-三苯硅基)苯基]-9-苯基-9H-咔唑(1b),其结构经1H NMR和元素分析表征.用UV-Vis,荧光光谱和循环伏安曲线研究了1a和1b的光电性能.     

达比加群酯中间体3-【【【2-{[(4-氰基苯基)氨基]甲基}-1-甲基-1H-苯并咪唑-5-基】羰基】(吡啶-2-基)氨基】丙酸乙酯的合成

以对氨基苯腈为起始原料,经胺化反应制得N-(4-氰基苯基)甘氨酸(4);4与N-[3-氨基-4-(甲基氨基)苯甲酰基]-N-2-吡啶-β-丙氨酸乙酯(5)经酰胺化后经闭环反应,合成了达比加群酯的关键中间体——3-【【【2-{[(4-氰基苯基)氨基]甲基}-1-甲基-1H-苯并咪唑-5-基】羰基】(吡啶-2-基)氨基】丙酸乙酯,总收率79.6%,其结构经~1H NMR和ESI-MS确证。     

N-(9,9-二苯基-9H-芴-2-基)-N,9-二苯基-9H-咔唑-2-胺的合成

以邻溴硝基苯为起始原料,经Suzuki偶联反应、Cadogan关环反应、Ullmam反应、Buchwald反应等合成了目标产物N-(9,9-二苯基-9H-芴-2-基)-N,9-二苯基-9H-咔唑-2-胺,其结构经¹H NMR、 ¹³C NMR和HR-MS(ESI)确证,并采用TG-DSC、 UV-Vis对产物的热稳定性能和光学性能进行了研究。      

新型联萘衍生物的合成及其光电性能

以咔唑和4,4’-二氨基-1,1’-联萘为初始原料,经重氮化反应、Ullmann反应、NBS亲电取代反应和Suzuki偶联反应,合成了两种新型空穴传输材料——4,4’-双[(9-对甲基苯基)-9H-3-咔唑基]-1,1’-联萘(4a)和4,4’-双[(9-对联苯基)-9H-3-咔唑基]-1,1’-联萘(4b),其结构经1H NMR和元素分析表征。研究了4a和4b在二氯甲烷中的UV和荧光性质。结果表明,4a和4b的最大发射波长分别为429 nm和427 nm。     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

Synthesis of Derivatives of 1-(9-Alkyl-9H-carbazol-3-yl)-4-carboxy-2-pyrrolidinones

Derivatives of 1-(9-alkyl-9H-carbazol-3-yl)-4-carboxy-2-pyrrolidinones (methyl esters, hydrazides) were synthesized. The condensation of the synthesized hydrazides with aromatic aldehydes, acetylacetone, and acetoacetic ester was studied. Structure of the obtained compounds was confirmed by IR and NMR spectroscopy. The specific characteristics of the substituents are discussed.     

A facile synthesis of novel benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones

A facile synthesis of hitherto unreported benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones (3a?Cl) is described. The synthesis mainly relies on the ultrasound-assisted Rap?CStoermer reaction of 3-chloroacetyl-9-methyl-9H-carbazole (1) with a variety of salicylaldehydes, as well as 2-hydroxy-1-naphthaldehyde (2) in CH₃CN, with the presence of PEG-400 as a catalyst. This procedure offers easy access to benzofuran-2-yl(carbazolyl)methanone derivatives in a short reaction time and the products are achieved in good yields.     

Mild synthesis of 5-(9-ethyl-9H-carbazol-3-yl)-N-aryl-1,3,4-thiadiazol-2-amines

An efficient synthetic method for heterocycles containing both carbazole and 1,3,4-thiadiazole moieties is described. 9-Ethyl-9H-carbazol-3-carbaldehyde reacted with 4-arylthiosemicarbazides, with acetic acid as catalyst, to give 1-(9-ethyl-9H-carbazol-3-yl)methylene-4-arylthiosemicarbazides, which were further treated with manganese dioxide at room temperature in acetone to give 5-(9-ethyl-9H-carbazol-3-yl)-N-aryl-1,3,4-thiadiazol-2-amines in good to high yield. This procedure has the advantages of mild conditions, easy separation, and simple manipulation.     

Synthesis,Crystal Structure and Photophysical Property of 2-(9H-carbazol-9-yl)-3-(2-(2,4,5-tri-(9H-carbazol-9-yl)-3,6-dicyanophenoxy)phenoxy) dibenzo[b,e][1,4]dioxine-1,4-dicarbonitrile

A purely organic compound 2-(9 H-carbazol-9-yl)-3-(2-(2,4,5-tri-(9 H-carbazol-9-yl)-3,6-dicyanophenoxy)phenoxy)dibenzo[b,e][1,4]dioxine-1,4-dicarbonitrile, C_(76) H_(40) N_8 O_4, was synthesized and characterized by NMR, UV-Vis, photoluminescenceand X-ray single-crystal structure analysis. The compound crystallizes in monoclinic system, space group P2_1/n with a = 11.6537(3), b = 34.9738(8), c = 15.5053(3) ?, β =101.992(2)°, V = 6181.6(2)?~3, Z = 4, M_r= 1129.18 g/mol, D_c =1.396 g/cm~3, F(000) =2672, μ = 2.239 mm~(–1), GOOF = 1.019, the final R = 0.0577 and wR= 0.1559 for 11925 observed reflections with I 2σ(I). The UV-vis absorption and fluorescence of the compound were discussed. The compound exhibitsyellow-green luminescence with maximum emission peak at 538 nm, and quantum yields of ф = 0.25 and 0.48 in air-equilibrated and degassed toluene at room temperature. Transient decay spectral studies show that compound 1 displays two component decay fashions with a short decay lifetime of 23 ns for the prompt fluoresce anda long decay lifetime of 3.8ms for thermally activated delayed fluorescence. In air-equilibrated toluene, only a short decay lifetime of 17 ns was observed.The experimental and computational results show thatthe emission of the compound originates from the CT excited states.     

基于N-乙基咔唑-2-乙烯基-8-羟基喹啉锌的黄绿色有机电致发光器件的性能

通过用一种既具有空穴传输特性又具有发光特性的新型荧光染料N-乙基咔唑-2-乙烯基-8-羟基喹啉锌((E)-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl) quinolato-zinc, CzHQZn)作为受主, 制备了结构为ITO/2T-NATA (30 nm)/CBP: 6%Ir(ppy)3:wCzHQZn(20 nm)/Alq3(50 nm)/LiF/Al(ITO: indium-tin oxide, 2T-NATA: 4,4',4'-{N,N-(2-naphthyl)-N-phenylamino}-triphenylamine, CBP: 4,4-N,N'-dicarbazole-biphenyl, Ir(ppy)3: factris (2-phenylpyridine) iridium, Alq3: tris(8-quinolinolato) aluminum; w 是CzHQZn 的质量分数)的黄绿色有机电致发光器件(OLEDs). 研究了掺杂体系在不同掺杂浓度(w=5%、10%、12%、15%)时的电致发光(EL)特性. 结果表明, CzHQZn 掺杂浓度为10%的器件在11 V 电压下实现了黄绿光发射, 色坐标为(0.4045, 0.5113), 最大发光亮度为16110 cd·m-2; 而在7 V电压下的最大发光效率为2.19 cd·A-1, 最大外量子效率为0.775%.     

Access to polycyclic carbazoles from ring-fused 2-(9H-carbazol-1-yl)anilines

Abstract

Nine 2-(9H-carbazol-1-yl)anilines with rings fused at the 3,4-position were acylated at the amino group with chloroacetyl, 3-chloropropanoyl, or 4-chlorobutyryl chloride, at yields of 85–99%. The resulting ω-chloroamides were exposed to potassium tert-butoxide in THF. All nine acetamides annulated exclusively at the carbazole N atom, giving benzodiazocinocarbazoles at 76–91% overall yield. The only propanamide prepared underwent α,β-elimination, giving the corresponding acrylamide at 70% overall yield. All nine butanamides annulated exclusively at the amide nitrogen, giving pyrrolidin-2-ones at 70–94% overall yield. Additionally, the 1-indanone derived carbazolylaniline followed the same annulation pattern, but the benzylic methylene group was oxidized, giving the corresponding fluorenones. The cyclohexanone-derived carbazolylaniline was also converted into a maleimide, which participated in a Diels-Alder reaction with cyclopentadiene. Attempts to replace the amino group in the starting material via diazotization were unsuccessful. Instead, a Widman-Stoermer reaction was observed, in which the diazonium group attacked the carbazole 2-position, giving the corresponding cinnoline.     

Synthesis and Crystal Structure of {4-[2-（9- Hexyl-9H-carbazol-3-yl）vinyl]phenyl} Dimethylamine

The title compound {4-[2-(9-hexyl-9H-carbazol-3-yl)vinyl]phenyl} dimethylamine has been synthesized by the well known Wittig reaction, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 47.87(2), b = 10.222(4), c = 9.612(4) , β = 92.401(9)o, V = 4699(3) 3, Z = 8, C28H32N2, Mr = 396.56, Dc = 1.121 g/cm3, F(000) = 1712 and μ(MoKa) = 0.065 mm-1. The final R and wR are 0.0793 and 0.1983, respectively for 3524 observed reflections with I > 2σ(I). In the title compound, the bond lengths are normal, and the crystal is stabilized by Van der Waals’ forces.     

Synthesis, Crystal Structure and Theoretical Studies of (E)-1-((9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl)methylene)thiosemicarbazide

A novel thiosemicarbazide derivative, (E)-1-(9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl) methylene)-thiosemicarbazide (CMT), was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.769(5), b = 8.279(5), c = 17.166(5) , β = 114.391(5)°, V = 1911.6(14) 3, Z = 4, F(000) = 784, Dc = 1.287 g/m3, Mr = 370.47, μ = 0.190 mm-1, the final R = 0.0390 and wR = 0.1358 for 1446 observed reflections with Ⅰ > 2σ(Ⅰ). The UV-vis absorption spectra of CMT were explained based on quantum chemical calculations, using time dependent density functional theory (TD-DFT) at the B3LYP/6-31G (d) level.     

双极绿色磷光主体材料1-甲基-3-[4-(9-咔唑基)苯基]-4-苯基喹啉-2(1H)-酮的合成与性能研究

设计并合成了一种基于喹诺酮衍生物的双极绿色磷光主体材料1-甲基-3-[4-(9-咔唑基)苯基]-4-苯基喹啉-2(1 H)-酮.计算发现,化合物的HOMO轨道的电子云位于咔唑基团,LUMO轨道的电子云位于喹诺酮基团,是一种良好的双极材料.化合物的磷光发射峰为515 nm(2.41 eV),符合绿色磷光主体材料的基本要求(>2.4 eV).热失重和差热分析结果表明,该化合物具有较高的热稳定性,分解温度和玻璃化转变温度分别为312℃和105℃.研究结果表明:该新型化合物是一种潜在的具有双极特性的绿色磷光主体材料.