WO2021068511A1 - 含S/Se/Te重原子的咔唑类室温磷光材料的合成及光电性能研究 - Google Patents
含S/Se/Te重原子的咔唑类室温磷光材料的合成及光电性能研究 Download PDFInfo
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- OMDNYWNFPNDGHN-UHFFFAOYSA-N O=C(c(cc1)ccc1-c1ccc[s]1)[n]1c2ccccc2c2c1cccc2 Chemical compound O=C(c(cc1)ccc1-c1ccc[s]1)[n]1c2ccccc2c2c1cccc2 OMDNYWNFPNDGHN-UHFFFAOYSA-N 0.000 description 1
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- the invention relates to the field of organic semiconductor materials, in particular to the synthesis and photoelectric performance research background technology of a carbazole room temperature phosphorescent material containing S/Se/Te heavy atoms.
- Organic room temperature phosphorescent materials have received widespread attention in the field of organic electroluminescence due to their wide sources, low cost, low toxicity, easy purification and easy modification of structure. Among them, it has broad application prospects in the fields of data security, organic light-emitting diodes (OLEDs), light-emitting sensors, and biological imaging. Studies have confirmed that by bonding the donor (D) unit carbazole and the acceptor (A) unit benzoyl group, the molecular structure can be modified by halogen heavy atoms to obtain a long-life D-A room temperature phosphorescent material.
- the building units of room temperature phosphorescent materials used for heterocyclic substitution are scarce, and currently mainly concentrated in tellurophene heterocyclic units, such as borate-substituted telluropheno ring (B-Te-6-B, Angew. Chem. Int. Ed. 2014, 53, 4587-4591), aryl-substituted telluropheno ring (Ar-Te-6-Ar, ACS. Appl. Mater. Interfaces., 201810, 15).
- B-Te-6-B Angew. Chem. Int. Ed. 2014, 53, 4587-4591
- aryl-substituted telluropheno ring Ar-Te-6-Ar, ACS. Appl. Mater. Interfaces., 201810, 15.
- tellurophene-based room temperature phosphorescent materials there are still limitations in the design and development of tellurophene-based room temperature phosphorescent materials.
- tellurophene-based phosphorescent materials At present, there is little research on tellurophene-based phosphorescent materials, and they are prone to self-quenching and oxygen quenching. Therefore, the design and development of new tellurophene-based room temperature phosphorescent materials It has very important research significance.
- the present invention aims at the challenges of the few types of tellurophene room temperature phosphorescent materials and their short light-emitting life, and provides a synthesis and photoelectric performance study of a carbazole room temperature phosphorescent material containing S/Se/Te heavy atoms.
- the present invention provides a D-A type carbazole-based room temperature phosphorescent material containing S/Se/Te heavy atoms, the phosphorescent material has the following structural formula I:
- A represents any one of S, Se, and Te.
- the D-A type carbazole-based room temperature phosphorescent material is PhCz-T, and the PhCz-T has the following structural formula of Formula II:
- the D-A carbazole-based room temperature phosphorescent material is PhCz-Se, and the PhCz-Se has a structural formula of the following formula III:
- the D-A type carbazole-based room temperature phosphorescent material is PhCz-Te, and the PhCz-Te has a structural formula of the following formula IV:
- the present invention also provides a method for preparing the above-mentioned D-A carbazole-based room temperature phosphorescent material, which includes the following steps:
- the X is:
- the structural formula of the aromatic heterocyclic monomer b is:
- the A represents any one of S, Se, Te,
- the Y represents -Sn(CH 3 ) 3 , -B(OR) 2 or Any one of them, where R represents hydrogen or a C 1 -C 6 alkyl group.
- step S1 the acylation reaction is carried out under alkaline conditions, and the base is selected from sodium hydroxide, potassium hydroxide, potassium tert-butoxide, methyl lithium,
- the base is selected from sodium hydroxide, potassium hydroxide, potassium tert-butoxide, methyl lithium
- tert-butyl lithium and lithium diisopropylamide is preferably lithium diisopropylamide.
- step S1 the acylation reaction is carried out in a solvent as a medium, and the solvent is selected from any one of water, ethanol, anhydrous tetrahydrofuran, and dioxane Or a combination thereof, preferably anhydrous tetrahydrofuran.
- step S1 the acylation reaction is carried out under the protection of an inert gas, and the inert gas is selected from nitrogen or argon.
- step S1 the reaction temperature of the acylation reaction is 0-40°C, preferably room temperature.
- step S1 in the acylation reaction, the mass ratio of carbazole, base and 4-halogen substituted benzoyl chloride is 1.0:1.1:1.5
- the palladium catalyst used in the coupling reaction is selected from the group consisting of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride and tris(dibenzylidene) Base acetone) any one or a combination of two palladium.
- the reaction solvent used in the coupling reaction is selected from any one or a combination of tetrahydrofuran, toluene and chlorobenzene.
- step S2 the coupling reaction is carried out under the protection of an inert gas, and the inert gas is selected from nitrogen or argon.
- step S2 the coupling reaction is carried out in a microwave reactor, and the microwave reaction temperature is 100-160°C, preferably 120°C-140°C.
- the coupling reaction is preferably a still reaction of the intermediate a and the monomethyl tin group substituted aromatic heterocyclic monomer b.
- step S2 the coupling reaction is that the mass ratio of intermediate a, monomethyltin substituted aromatic heterocyclic monomer b and palladium catalyst is 1:1.5:0.01.
- the present invention also provides a D-A type carbazolyl derivative with the structure of Formula I to Formula IV as a room temperature phosphorescent material.
- the present invention provides a D-A type carbazolyl room temperature phosphorescent material, which uses 4-halogen substituted carbazolyl derivatives as important intermediates, and is substituted with different heteroatoms sulfur, selenium and tellurium atoms.
- the tellurophene-substituted carbazolyl derivative has room temperature phosphorescence properties, and is a new type of tellurophene-based phosphorescent material molecule.
- the present invention provides a D-A carbazole-based room temperature phosphorescent material, in which tellurophene is used as a substituent group, which can significantly reduce the LUMO energy level of the compound. Compared with chalcogenide homologs, tellurophene has a narrower optical band gap and higher electron mobility.
- the present invention provides a D-A type carbazole-based room temperature phosphorescent material, the D-A type structure of which is conducive to the regulation of molecular energy levels and effective intramolecular electron transfer.
- Such compound molecules have good solubility and thermal stability, and meet the test requirements of organic light-emitting diodes.
- the introduction of different degrees of heavy atom effects in the molecule effectively regulates the luminescence properties of each compound.
- the present invention provides a method for preparing DA type carbazole-based room temperature phosphorescent material, which has the advantages of low-cost and easy-to-obtain reaction raw materials, mild synthesis conditions, short synthesis route, simple and efficient synthesis method, and good repeatability. It can be popularized and enlarged. Synthesis and production.
- Figure 1 shows the single crystal structure of the D-A carbazole compound containing S/Se/Te heteroatoms in Examples 1-3 of the present invention.
- Example 2 is the ultraviolet-visible-near infrared absorption spectrum of the sulfur heteroatom-containing D-A carbazole compound PhCz-T in chloroform solution and solid film in Example 1 of the present invention.
- Fig. 3 is the ultraviolet-visible-near infrared absorption spectrum of the D-A carbazole-based room temperature phosphorescent material PhCz-Se containing selenium heteroatoms in chloroform solution and solid film in Example 2 of the present invention.
- Example 4 is the ultraviolet-visible-near-infrared absorption spectrum of the D-A carbazole-based room temperature phosphorescent material PhCz-Te containing tellurium heteroatoms in chloroform solution and solid film in Example 3 of the present invention.
- Fig. 5 is a thermal weight loss curve of D-A carbazole compounds PhCz-T, PhCz-Se and PhCz-Te containing S/Se/Te heteroatoms in Experimental Example 1 of the present invention.
- Fig. 6 is the cyclic voltammetry curve of the film state of the D-A carbazole compounds PhCz-T, PhCz-Se and PhCz-Te containing S/Se/Te heteroatoms in the acetonitrile solution in Experimental Example 2 of the present invention.
- Fig. 7 shows the emission spectra of D-A carbazole compounds containing S/Se/Te heteroatoms at different excitation wavelengths in Example 3 of the present invention.
- FIG. 8 is a temperature-variable emission spectrum and life attenuation curve of a D-A type carbazole-based room temperature phosphorescent material containing Se/Te heteroatoms in Example 4 of the present invention.
- a D-A type carbazolyl compound PhCz-T of the present invention has the general structural formula of formula I:
- the single crystal structure of the compound PhCz-T obtained by the gas-liquid diffusion method is shown in Figure 1, and the single crystal shape is a white bar.
- Figure 2 shows the ultraviolet-visible-near-infrared absorption spectrum of the chloroform solution and solid film of the compound PhCz-T substituted with S heteroatoms.
- the compound PhCz-T exhibits an absorption range of 275-400nm
- the film absorption maximum absorption sideband value is about 386nm
- a D-A type carbazolyl compound PhCz-Se of the present invention has the general structural formula of Formula II:
- MALDI-TOF-MS m/z[M] + calcd for(C 23 H 15 NOSe): 401.03; found: 401.0.
- the single crystal structure of the compound PhCz-Se obtained by the gas-liquid diffusion method is shown in Figure 1, and the single crystal shape is white needle-like.
- Figure 3 shows the ultraviolet-visible-near-infrared absorption spectrum of the compound PhCz-Se in chloroform solution and solid film.
- the compound PhCz-Se exhibits an absorption range of 275-400nm
- the film absorption maximum absorption sideband value is about 404nm
- a D-A type carbazolyl compound PhCz-Te of the present invention has the general structural formula of Formula III:
- the single crystal structure of the compound PhCz-Te obtained by the gas-liquid diffusion method is shown in Figure 1.
- the single crystal shape is light yellow flakes, and there are two single crystal configurations of tellurium atoms facing inward and tellurium atoms facing outward.
- the product has the correct structure and is the compound PhCz-Te.
- Figure 4 shows the ultraviolet-visible-near infrared absorption spectrum of the compound PhCz-Te in chloroform solution and solid film.
- the compound PhCz-Te exhibits an absorption range of 275-400nm
- the film absorption maximum absorption sideband value is about 408nm
- Figure 5 shows the DA type carbazolyl derivative PhCz- Thermal weight loss curves of T, PhCz-Se and PhCz-Te in air. It can be seen from Figure 5 that the three compounds have good thermal stability, and their decomposition temperatures at 5% thermal weight loss all exceed 250°C, which meets the requirements of optoelectronic device construction and testing.
- Figure 6 shows the cyclic voltammetry curves of compounds PhCz-T, PhCz-Se and PhCz-Te in acetonitrile solution.
- the test conditions are: a three-electrode working system is used to measure the oxidation-reduction potential, a glassy carbon electrode is selected as the working electrode, Ag/AgCl is the reference electrode, the platinum wire electrode is the counter electrode, and the concentration is 0.1mol/L tetrabutylhexafluorophosphate
- the acetonitrile solution of ammonium was used as the supporting electrolyte, and ferrocene was used as the internal standard (0.5V vs. Ag/AgCl).
- the compound PhCz-Te has a narrower electrochemical band gap compared to the compounds PhCz-T and PhCz-Se.
- Figure 7 shows the emission spectra of the compounds PhCz-T, PhCz-Se and PhCz-Te crystals under different wavelength excitation conditions and their corresponding luminescence lifetimes.
- the test conditions are: the compounds PhCz-T, PhCz-Se and PhCz-Te obtain different emission spectra and luminescence lifetime decay curves at different emission wavelengths at 408 nm, 384 nm and 410 nm as excitation wavelengths, respectively.
- the luminescence lifetimes of the three compound crystals at short wavelengths are in the order of ps ⁇ ns, which are attributed to fluorescence emission; in the long wavelength range, there are only the emission peaks of PhCz-Se and PhCz-Te crystals, and their luminescence lifetimes are respectively 113.1 ⁇ s (@590nm) and 12.2 ⁇ s (@650nm).
- the material preparation method provided by the invention has the characteristics of simple, high-efficiency, easy-to-obtain raw materials and the like. By changing the substitution of heteroatoms with different atomic numbers, we can effectively control the luminescence performance of the target compound, analyze the internal relationship between the single crystal structure and the luminescence performance of organic semiconductor materials, and provide theoretical guidance for the future design of high-performance room temperature phosphorescent materials.
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Abstract
本发明公开了一种D-A型咔唑基衍生物的制备方法及其发光性质,其中咔唑基衍生物的结构通式为 (I) 该D-A型结构以咔唑为给体单元,苯甲酰基为受体单元,三种材料都具有良好的溶解性和热稳定性,本发明的咔唑基衍生物制备方法主要由4-碘代苯甲酰基与五元杂环单边锡化物通过Stille偶联反应制备。本发明所提供的制备方法路线简单,步骤少,生产成本低。更重要的是,通过不同重量的杂原子取代,调控了该类材料的发光性能,实现了由荧光到磷光的转变,因而在有机发光二极管和生物成像等领域中具有广阔的应用前景。
Description
本发明涉及有机半导体材料领域,尤其涉及一种含S/Se/Te重原子的咔唑类室温磷光材料的合成及光电性能研究背景技术。
有机室温磷光材料由于具有来源广、成本低、毒性小、易于提纯和结构易修饰等特点,在有机电子发光领域已受到广泛关注。其中在数据安全保密、有机发光二极管(OLEDs)、发光传感器、生物成像等领域中具有广阔的应用前景。研究证实:将给体(D)单元咔唑与受体(A)单元苯甲酰基键合反应,通过卤素重原子在分子结构中进行修饰,可获得具有长寿命的D-A型室温磷光材料。相比卤素重原子,用于杂环取代的室温磷光材料构建单元稀缺,目前主要集中在碲吩杂环单元,譬如硼酸酯取代的碲吩并环(B-Te-6-B,Angew.Chem.Int.Ed.2014,53,4587–4591),芳基取代的碲吩并环(Ar-Te-6-Ar,ACS.Appl.Mater.Interfaces.,201810,15)。然而,碲吩类室温磷光材料的设计与开发依然存在局限性,目前对于碲吩类磷光材料研究较少,而且易于发生自猝灭和氧猝灭,因此设计开发新型的碲吩类室温磷光材料具有十分重要的研究意义。
发明内容
本发明针对碲吩类室温磷光材料种类少及其发光寿命短等挑战,提供一种含S/Se/Te重原子的咔唑类室温磷光材料的合成与光电性能研究。为解决上述技术问题,本发明提供了一种含S/Se/Te重原子的D-A型咔唑类室温磷光材料,所述磷光材料具有以下式I的结构式::
所述式I中,A表示S、Se、Te中的任意一种。
上述的D-A型咔唑类室温磷光材料,优选的,所述D-A型咔唑类室温磷光材料为PhCz-T,所述PhCz-T具有以下式II的结构式:
上述的D-A型咔唑类室温磷光材料,优选的,所述D-A型咔唑类室温磷光材料为PhCz-Se,所述PhCz-Se具有以下式III的结构式:
上述的D-A型咔唑类室温磷光材料,优选的,所述D-A型咔唑类室温磷光材料为PhCz-Te,所述PhCz-Te具有以下式IV的结构式:
除此之外,本发明还提供了一种上述D-A型咔唑类室温磷光材料的制备方法,包括以下步骤:
S1、将咔唑与4-卤代苯甲酰氯进行酰化反应,得到中间体a;
S2、将所述中间体a与芳香杂环单体b在钯催化剂的作用下进行偶联反应,得到具有式I结构式的D-A型咔唑基衍生物;
其中,所述中间体a的结构式为:
所述X为:
F、Cl、Br、I中的任意一种;
所述芳香杂环单体b的结构式为:
其中,所述A表示S、Se、Te中的任意一种,
在本发明的技术方案中:在步骤S1中,所述酰化反应是在碱性条件下进行的,所述的碱选自氢氧化钠、氢氧化钾、叔丁醇钾、甲基锂、叔丁基锂、二异丙基氨基锂中的一种,优选为二异丙基氨基锂。
在本发明的技术方案中:在步骤S1中,所述酰化反应是在溶剂作为介质中进行的,所述的溶剂选自水、乙醇、无水四氢呋喃、二氧六环中的任意一种或其组合,优选为无水四氢呋喃。
在本发明的技术方案中:在步骤S1中,所述酰化反应是在惰性气体保护下进行反应的,所述惰性气体选自氮气或者氩气。
在本发明的技术方案中,在步骤S1中,所述酰化反应的反应温度为0-40℃,优选为室温。
在本发明的技术方案中,在步骤S1中,所述酰化反应中,咔唑、碱与4-卤素取代的苯甲酰氯的质量比为1.0︰1.1︰1.5
在本发明的技术方案中:在步骤S2中,所述偶联反应所用的钯催化剂选自四(三苯基膦)钯、双(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中的任意一种或其组合。
在本发明的技术方案中:在步骤S2中,所述偶联反应所用的反应溶剂选自四氢呋喃、甲苯和氯苯中的任意一种或其组合。
在本发明的技术方案中:在步骤S2中,所述偶联反应是在惰性气体保护下进行的,所述惰性气体选自氮气或者氩气。
在本发明的技术方案中:在步骤S2中,所述偶联反应是在微波反应器中进行的,所述微波反应温度为100~160℃,优选为120℃~140℃。
在本发明的技术方案中,在步骤S2中,所述偶联反应是优选为中间体a、单甲基锡基取代芳香杂环单体b发生still反应。
在本发明的技术方案中:在步骤S2中,所述偶联反应是中间体a、单甲基锡基取代芳香杂环单体b与钯催化剂的质量比为1︰1.5︰0.01。
特别地,在本发明的技术方案中包含了如下反应步骤:
S1:在氮气保护下,将咔唑和四氢呋喃溶剂混合,在低温-78℃条件下搅拌30分钟,再逐滴加入二异丙基氨基锂(LDA)在-78℃搅拌1小时,然后升温至40℃,搅拌反应1小时;紧接着在-78℃和氮气保护下,逐滴加入4-碘代苯甲酰氯,混合物升温至室温反应10~16小时得到中间体a。进一步的,所述咔唑、LDA与4-卤素取代的苯甲酰氯的质量比为1.0︰1.1︰1.5。
S2:将中间体a、单甲基锡基取代芳香杂环单体b、溶剂和钯催化剂混合,在氮气保护下以120℃~140℃在微波反应器中搅拌4~6小时得到D-A型咔唑类室温磷光材料。进一步的,所述中间体a、单甲基锡基取代芳香杂环单体b与钯催化剂的质量比为1︰1.5︰0.01。
除此之外,本发明还提供了一种具有式I至式IV结构的D-A型咔唑基衍生物作为室温磷光材料的应用。
与现有技术相比,本发明的优点在于:
(1)本发明提供了一种D-A型咔唑基室温磷光材料,以4-卤素取代的咔唑基衍生物作为重要中间体,进行了不同杂原子硫、硒和碲原子的取代。本发明中碲吩取代的咔唑基衍生物具有室温磷光性质,且是一类新型的碲吩基磷光材料分子。
(2)本发明提供了一种D-A型咔唑基室温磷光材料,其中以碲吩作为取代基团,可以显著降低化合物的LUMO能级。相比硫族同系物,碲吩具有更窄的光学带隙和更高的电子迁移率。
(3)本发明提供了一种D-A型咔唑基室温磷光材料,其D-A型结构有利于调控分子能级和进行有效地分子内电子传递。该类化合物分子具有良好的溶解性和热稳定性,满足有机发光二极管的测试要求。其次,在分子中引入不同程度的重原子效应有效地调控了各化合物的发光性质。
(4)本发明提供了一种D-A型咔唑基室温磷光材料的制备方法,具有反应原料廉价易得、合成条件温和、合成路线简短、合成方法简单高效以及重复性好等优点,可推广放大合成与生产。
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整的描述。
图1为本发明实施例1-3中以含S/Se/Te杂原子的D-A型咔唑类化合物的单晶结构。
图2为本发明实施例1中含硫杂原子的D-A型咔唑类化合物PhCz-T在氯仿溶液和固态薄膜的紫外–可见–近红外吸收光谱。
图3为本发明实施例2中含硒杂原子的D-A型咔唑类室温磷光材料PhCz-Se在氯仿溶液和固态薄膜的紫外–可见–近红外吸收光谱。
图4为本发明实施例3中含碲杂原子的D-A型咔唑类室温磷光材料PhCz-Te在氯仿溶液和固态薄膜的紫外–可见–近红外吸收光谱。
图5为本发明实验例1中含S/Se/Te杂原子的D-A型咔唑类化合物PhCz-T、PhCz-Se和PhCz-Te的热失重曲线。
图6为本发明实验例2中含S/Se/Te杂原子的D-A型咔唑类化合物PhCz-T、PhCz-Se和PhCz-Te的薄膜态在乙腈溶液中测定的循环伏安曲线。
图7为本发明实施例3中以含S/Se/Te杂原子的D-A型咔唑类化合物在不同激发波长处的发射光谱。
图8为本发明实施例4中以含Se/Te杂原子的D-A型咔唑类室温磷光材料的变温发射光谱及寿命衰减曲线。
以下结合说明书附图和具体优选的实施例对本发明作进一步描述,但并不因此而限制本发明的保护范围。以下所述实施例旨在便于对本发明的理解,而对其不起任何限定作用。所述方法如无特别说明均为常规方法。所述反应物料如无特别说明均能从公开商业途径购买而得。
实施例1:
一种本发明的D-A型咔唑基化合物PhCz-T具有式I的结构通式:
PhCz-T的合成路线为:
具体包括以下步骤:
(1)中间体a的合成:氮气保护下,向100mL的Schlenk中加入咔唑(1.0g,6.0mmol)和无水四氢呋喃(30mL),然后把反应瓶放置–78℃的低温仪中。在–78℃下,向反应瓶中缓慢滴加二异丙基氨基锂(2.0M,3.3mL),在–78℃下反应1h,再缓慢回温至–40℃搅拌1h。然后,在–78℃条件下一次性注入4-碘代苯甲酰氯的四氢呋喃溶液(2.4g,9mmol),最后在室温下搅拌过夜。混合物用乙酸乙酯和水萃取、干燥、过滤、旋干。粗产物经过硅胶色谱柱提纯(石油醚:乙酸乙酯=10:1)得到白色固体1.8g即中间体a(收率=75%)。
以碘原子取代的中间体a为例,其结构表征数据如下:
1H NMR(400MHz,CDCl
3),δ(ppm):8.04-8.00(m,2H),7.91-7.87(m,2H),7.54-7.51(m,2H),7.47-7.44(m,2H),7.39-7.32(m,4H);
13C NMR(100MHz,CDCl
3),δ(ppm):168.80,139.05,138.28,135.12,130.73,126.96,126.17,123.72,120.03,115.80,99.79.
Elm.Anal.Calcd for C
19H
12INO Cal.:C,57.45;H,3.05;N,3.53.Found:C,57.41;H,3.03;N,3.45.
MALDI-TOF-MS:m/z[M]
+calcd for(C
19H
12INO):397.21;found:397.3.
由上可知,该化合物结构正确,为所示中间体a:(9氢-咔唑-9-基)-(4-碘苯基)甲酮。
(2)化合物PhCz-T的合成:在10mL微波管中,加入碘代咔唑基中间体(1.0g,2.5mmol)、噻吩单边锡化物(0.93g,3.7mmol)和6mL甲苯。氮气条件下置换氧气20min,然后加入催化剂四三苯基膦钯(10mg),再鼓氮气10min,封装微波盖,在120℃下反应4h。冷却至室温后,用二氯甲烷萃取,无水硫酸镁干燥、抽滤、旋干。通过硅胶柱色谱法纯化混合物,以正己烷/二氯甲烷混合 物(5:1)作为洗脱剂纯化,最后得到534mg白色粉末即PhCz-T(收率=60%)。
化合物PhCz-T的结构表征数据如下:
1H NMR(400MHz,CDCl
3),δ(ppm):8.04-8.02(m,2H),7.78-7.73(m,4H),7.60-7.58(m,2H),7.49-7.48(dd,J
1=8Hz,J
2=3.6Hz,1H),7.41-7.32(m,5H),7.16-7.14(m,1H);
13C NMR(100MHz,CDCl
3)δ(ppm):169.05,142.81,139.15,138.34,134.04,130.11,128.42,126.76,126.48,125.98,125.88,124.66,123.37,119.87,115.74.
Elm.Anal.Calcd for C
23H
15NOS Cal.:C,78.16;H,4.28;N,3.96.Found:C,78.19;H,4.20;N,4.09.
MALDI-TOF-MS:m/z[M]
+calcd for(C
23H
15NOT):353.08;found:353.1.
通过气液扩散法获得化合物PhCz-T的单晶结构如图1所示,其单晶形状为白色条状。
由上可知,该产物结构正确,为化合物PhCz-T。
对化合物PhCz-T进行吸收光谱性质的测定:图2为含S杂原子取代的化合物PhCz-T的三氯甲烷溶液和固态薄膜的紫外–可见–近红外吸收光谱。在三氯甲烷溶液和固态薄膜中,化合物PhCz-T展现出275~400nm的吸收范围,其薄膜吸收最大吸收边带值为386nm左右,相应的光学带隙为E
g
opt=3.21eV(光学带隙根据公式E
g
opt=1240/λ计算,其中E
g
opt为光学带隙,λ为薄膜吸收最大吸收边带值)。
实施例2:
一种本发明的D-A型咔唑基化合物PhCz-Se具有式Ⅱ的结构通式:
PhCz-Se的合成路线为:
具体的合成步骤为:
(1)中间体a的合成:参照上述实施例1的合成方法合成。
(2)化合物PhCz-Se的合成:在10mL微波瓶中,加入碘代咔唑基中间体(0.85g,2.1mmol)、硒吩单边锡化物(1.0g,3.4mmol)和6mL甲苯。氮气条件下置换氧气20min,然后加入催化剂四三苯基膦钯(8mg),再鼓氮气10min,封装微波盖,在120℃下反应4h。冷却至室温后,用二氯甲烷萃取,无水硫酸镁干燥、抽滤、旋干。通过硅胶柱色谱法纯化混合物,以正己烷/二氯甲烷混合物(5:1)作为洗脱剂纯化,最后得到653mg的白色粉末(收率=76%)。
化合物PhCz-Se的结构表征数据如下:
1H NMR(400MHz,CDCl
3)δ(ppm):8.08-8.06(d,J=8.0Hz,1H),8.05-8.01(m,2H),7.75-7.69(dd,J
1=16.0Hz,J
2=8.0Hz,4H),7.65(d,J=4.0Hz,1H),7.61-7.57(m,2H),7.40-7.32(m,5H);
13C NMR(100MHz,CDCl
3)δ(ppm):169.04,149.09,140.31,139.15,134.13,131.87,130.96,130.14,126.93,126.77,126.40,125.99,123.39,119.88,115.75.
Elm.Anal.Calcd for C
23H
15NOSe Cal.:C,69.00;H,3.78;N,3.50.Found:C,69.47;H,3.91;N,3.53.
MALDI-TOF-MS:m/z[M]
+calcd for(C
23H
15NOSe):401.03;found:401.0.
通过气液扩散法获得化合物PhCz-Se的单晶结构如图1所示,其单晶形状为白色针状。
由上可知,该产物结构正确,为化合物PhCz-Se。
对化合物PhCz-Se进行吸收光谱性质的测定:图3为化合物PhCz-Se的三氯甲烷溶液和固态薄膜的紫外–可见–近红外吸收光谱。在三氯甲烷溶液和固态薄膜中,化合物PhCz-Se展现出275~400nm的吸收范围,其薄膜吸收最大吸收边带值为404nm左右,相应的光学带隙为E
g
opt=3.07eV(光学带隙根据公式E
g
opt=1240/λ计算,其中E
g
opt为光学带隙,λ为薄膜吸收最大吸收边带值)。
实施例3:
一种本发明的D-A型咔唑基化合物PhCz-Te具有式Ⅲ的结构通式:
PhCz-Te的合成路线为:
具体的合成步骤为:
(1)中间体a的合成:参照上述实施例1的合成方法合成。
(2)化合物PhCz-Te的合成:在10mL微波瓶中,放入碘代咔唑基中间体(0.8g,2.0mmol)、碲吩单边锡化物(1.0g,3.0mmol)和6mL氯苯。氮气条件下置换氧气20min,然后加入催化剂四三苯基膦钯(8mg),再鼓氮气10min,封装微波盖,在140℃下反应4h。冷却至室温后,用二氯甲烷萃取,无水硫酸镁干燥、抽滤、旋干。通过硅胶柱色谱法纯化混合物,以正己烷/二氯甲烷混合物(3:1)作为洗脱剂纯化,最后得到435mg的浅黄色粉末(收率=48%)。
化合物PhCz-Te的结构表征数据如下:
1H NMR(400MHz,CDCl
3)δ(ppm):8.96-8.94(d,J=8.0Hz,1H),8.04-7.99(m,3H),7.89-7.87(m,1H),7.63-7.61(d,J=8.0Hz,2H),7.60-7.59(m,4H),7.38-7.33(m,4H);
13C NMR(100MHz,CDCl
3)δ(ppm):169.04,147.88,144.06,139.14,138.91,134.98,134.13,130.18,127.87,127.14,126.76,125.97,123.37,119.87,115.74.
Elm.Anal.Calcd for C
23H
15NOTe Cal.:C,61.53;H,3.37;N,3.12.Found:C,63.48;H,4.58;N,2.87.
MALDI-TOF-MS:m/z[M]
+calcd for(C
23H
15NOTe):451.02;found:451.3.
通过气液扩散法获得化合物PhCz-Te的单晶结构如图1所示,其单晶形状为浅黄色片状,且存在碲原子朝内和碲原子朝外两种单晶构型。
由上可知,该产物结构正确,为化合物PhCz-Te。
对化合物PhCz-Te进行吸收光谱性质的测定:图4为化合物PhCz-Te的三氯甲烷溶液和固态薄膜的紫外–可见–近红外吸收光谱。在三氯甲烷溶液和固态薄膜中,化合物PhCz-Te展现出275~400nm的吸收范围,其薄膜吸收最大吸收边带值为408nm左右,相应的光学带隙为E
g
opt=3.04eV(光学带隙根据公式E
g
opt=1240/λ计算,其中E
g
opt为光学带隙,λ为薄膜吸收最大吸收边带值)。
实验例1:
将实施例1、实施例2和实施例3的D-A型咔唑基衍生物PhCz-T、PhCz-Se和PhCz-Te进行热稳定性的测定:图5为D-A型咔唑基衍生物PhCz-T、PhCz-Se和PhCz-Te在空气中的热失重曲线。从图5中可知:三个化合物具有良好的热稳定性,其热失重5%时的分解温度均超过250℃,满足光电器件构造和测试要求。
实验例2:
对实施例1、实施例2和实施例3中化合物PhCz-T、PhCz-Se和PhCz-Te的电化学性质进行测定:
图6为化合物PhCz-T、PhCz-Se和PhCz-Te在乙腈溶液中的循环伏安曲线。测试条件为:采用三电极工作体系测定氧化还原电位,选取玻璃碳电极作为工作电极,Ag/AgCl为参比电极,铂丝电极作为对电极,浓度为0.1mol/L的四丁基六氟磷酸铵的乙腈溶液作为支持电解质,二茂铁作为内标(0.5Vvs.Ag/AgCl)。扫描范围为-2.0V~2.0V,扫描速率为0.1mV/s。从图5的结果可知:化合物PhCz-T、PhCz-Se和PhCz-Te的LUMO能级分别为-2.95eV、-2.96eV和-2.98eV;化合物PhCz-T、PhCz-Se和PhCz-Te的HOMO能级分别为-6.06eV、-6.03eV和-5.65eV;能级带隙分别为E
g=3.11eV、E
g=3.07eV和E
g=2.67eV。结果表明:随着杂原子半径逐渐增大,其HOMO能级逐渐升高,LUMO能级逐渐降低。因而,相比化合物PhCz-T和PhCz-Se,化合物PhCz-Te具有更窄的电化学带隙。
实验例3:
对实施例1、实施例2和实施例3中化合物PhCz-T、PhCz-Se和PhCz-Te的发射光谱及发光寿命进行测定:
图7为化合物PhCz-T、PhCz-Se和PhCz-Te晶体在不同波长激发条件下的发射光谱及其对应的发光寿命。测试条件为:化合物PhCz-T、PhCz-Se和PhCz-Te分别在408nm、384nm和410nm为激发波长下得到不同的发射光谱以及不同发射波长处的发光寿命衰减曲线。由图可知:三种化合物晶体在短波长处的发光寿命数量级为ps~ns,归属于荧光发射;在长波长范围内,仅有PhCz-Se和PhCz-Te晶体的发射峰,其发光寿命分别为113.1μs(@590nm)和12.2μs(@650nm)。
实验例4:
由于晶体PhCz-Se和PhCz-Te在长波长处的寿命均为微秒级,存在热激活延迟荧光的可能性。为了进一步确定两种化合物的发光性质,因而测试了化合物 PhCz-Se和PhCz-Te在晶体态的变温发射光谱及其对应的变温寿命衰减如图8所示。由图可知:随着测试温度的降低,化合物PhCz-Se和PhCz-Te的PL强度逐渐增强。相应地,随着温度的降低,两种化合物的发光寿命均逐渐增长,因而其发光性能属于磷光发射。结果表明:由于重原子效应的强弱,化合物PhCz-T仅表现出荧光发射,而化合物PhCz-Se和PhCz-Te均表现出荧光和室温磷光双发射性质。
以上研究结果证实:本发明提供的式(I)、式(II)和式(Ⅲ)所示含S/Se/Te杂原子取代的咔唑基衍生物是一类具有荧光或磷光发光性质的D-A型有机半导体材料。本发明所提供的材料制备方法具有简单高效、原料易得等特点。我们通过改变不同原子序数的杂原子取代,实现对目标化合物发光性能的有效调控,分析单晶结构与有机半导体材料发光性能之间的内在关联,为今后设计高性能的室温磷光材料提供理论指导。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制。虽然本发明已以较佳实施例揭示如上,然而并非用以限定本发明。任何熟悉本领域的技术人员,在不脱离本发明的精神实质和技术方案的情况下,都可利用上述揭示的方法和技术内容对本发明技术方案做出许多可能的变动和修饰,或修改为等同变化的等效实施例。因此,凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所做的任何简单修改、等同替换、等效变化及修饰,均仍属于本发明技术方案保护的范围内。
Claims (10)
- 根据权利要求5所述的制备方法,其特征在于:在步骤S1中,所述酰化反应是在碱性条件下进行的,所述的碱选自氢氧化钠、氢氧化钾、叔丁醇钾、甲基锂、叔丁基锂、二异丙基氨基锂中的一种,优选为二异丙基氨基锂。
- 根据权利要求5所述的制备方法,其特征在于:在步骤S1中,所述酰化反应是在溶剂作为介质中进行的,所述的溶剂选自水、乙醇、无水四氢呋喃、二氧六环中的任意一种或其组合,优选为无水四氢呋喃。
- 根据权利要求5所述的制备方法,其特征在于:在步骤S2中,所述偶联反应所用的钯催化剂选自四(三苯基膦)钯、双(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中的任意一种或其组合。
- 根据权利要求5所述的制备方法,其特征在于:在步骤S2中,所述偶联反应所用的反应溶剂选自四氢呋喃、甲苯和氯苯中的任意一种或其组合。
- 根据权利要求1-4任一项所述的D-A型咔唑基衍生物作为室温磷光材料的应用。
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Publication number | Priority date | Publication date | Assignee | Title |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060068221A1 (en) * | 2002-08-28 | 2006-03-30 | Canon Kabushiki Kaisha | Organic light-emitting device |
CN108069951A (zh) * | 2016-11-08 | 2018-05-25 | 华南理工大学 | 一类基于苯甲酰基衍生物的有机电致发光材料及制备方法 |
CN110305121A (zh) * | 2019-07-25 | 2019-10-08 | 硕明(常州)光源科技有限公司 | 一种n-酰基咔唑类化合物及其制备方法和应用 |
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Non-Patent Citations (2)
Title |
---|
HAO CHEN ET AL.: "Toward Achieving Single-Molecule White Electroluminescence from Dual Emission of Fluorescence and Phosphorescence", CHEMISTRY OF MATERIALS, vol. 32, no. 9, 22 April 2020 (2020-04-22), XP055802037 * |
YANG LEI; QIN LINQING; XU YUNXIAO; ZHANG HUOTIAN; LV LEI; CHEN KEPENG; SUI XINYU; ZHONG YANGGUANG; GUO YUAN; GAO FENG; ZHAO JIANZH: "Sulfur vs. tellurium: the heteroatom effects on the nonfullerene acceptors", SCIENCE CHINA CHEMISTRY; THE FRONTIERS OF CHEMICAL BIOLOGY AND SYNTHESIS, SCIENCE CHINA PRESS, SIENCE CHINA PRESS, vol. 62, no. 7, 29 March 2019 (2019-03-29), Sience China Press, pages 897 - 903, XP036816491, ISSN: 1674-7291, DOI: 10.1007/s11426-019-9462-4 * |
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