溶液加工型自主体热活化延迟荧光材料的研究进展

十年来,作为第三代有机发光二极管(organic light-emitting diodes, OLED)发光材料的热活化延迟荧光(thermally activated delayed fluorescence, TADF)材料备受学术界和产业界的广泛关注. TADF分子由于单重态与三重态之间的能级差较小,当受到环境热激活时,三重态激子可以通过反系间窜越转化为单重态,从理论上讲,可以实现100%的激子利用率.这一特性使得OLED器件外量子效率显著提高.溶液加工法具有成本低、方法简单、材料利用率高、可大面积生产等优势,是柔性及印刷OLED器件制备工艺的理想候选.具有良好的电荷传输能力的主体材料能有效降低激子密度和促进能量高效传递.利用自主体TADF材料制备的溶液加工型器件能有效平衡载流子传输和提升器件性能,同时在使用过程中可避免相分离,保持薄膜的均匀性和提高器件的稳定性.本综述总结了溶液加工型自主体TADF材料的研究进展.首先介绍了TADF材料的基本原理和研究意义,强调了溶液加工型自主体TADF材料在显示器件和照明器件等方面的应用潜力.然后详细讨论了溶液加工型自主体TADF材料的不同分...     

分子筛限域碳点实现超长寿命热活化延迟荧光

正热活化延迟荧光(TADF)材料由于其较小的单重态-三重态能级差(ΔEST),三重态可通过反系间窜跃转向单重态而发出延迟荧光,从而获得潜在的高荧光量子效率。这类材料独特的发光性能使其在光电器件、生物成像、传感等应用方面展现出优势~(1,2)。但目前报道的TADF材料主要集中于纯有机材料和有机金属络合物,其延迟荧光寿命     

蓝光热激子材料的研究进展

热激子荧光材料由于交错的能级排列,激子在电致发光过程中可由高位三重态通过反向系间窜跃转换到单重态,从而最大限度利用三重态激子,实现理论100%的最大内量子效率,这不仅突破了传统荧光材料和三重态-三重态上转换发光材料在激子利用上的限制,而且克服了热活化延迟荧光(TADF)材料在高电流密度下效率滚降严重的问题,因而在电致发光上显现出独特的优势.蓝光长期以来是有机光电全彩显示的短板.蓝光显示上,磷光材料和TADF材料的色纯度和稳定性往往不尽如人意,而热激子材料可实现更高品质的蓝光发射,即使在深蓝领域也能表现出不俗的器件性能.系统地综述了蓝光热激子材料的发光机理、设计准则以及近年来具有代表性的研究成果,并对其发展趋势进行展望.     

有机-过渡金属配合物的三重态发光问题

近年来,随着OLED器件的发展,有关有机-过渡金属配合物的三重态发光问题受到人们广泛的关注。这不仅是与电致发光器件效率的提高相关联,同时也是一个在光物理研究中值得深入研究的课题.文章对有机-金属化合物激发态的能级分裂,以及发光三重态亚态的零场-分裂(ZFS)等进行了讨论,对具不同电子构型中心金属离子,例如八面体结构与平面四方形构型结构等与它们光物理行为间的关系进行了讨论.特别对这类体系的发光三重态在自旋轨道偶合作用(SOC)和构型相互作用(CI)的影响下,导致单重态与三重态的混合和促进从最低三重态到基态的发光跃迁进行了讨论.     

电子给体-受体型热活化延迟荧光蓝光材料研究进展

热活化延迟荧光材料由于其最低激发单重态和最低激发三重态之间的能级差较小,三重态激子可以通过反向系间窜越过程上转换到单重态,实现无贵金属添加的三重态激子参与的荧光发射,大大提高了发光效率,解决了传统荧光有机发光二极管(OLED)内/外量子效率(≤25%/≤5%)低下的问题;与磷光OLED相比,避免了使用贵金属,在造价方面具有更大优势.在类型众多的热活化延迟荧光(TADF)材料中,由于电子给体-受体型分子合成简单,性能出众而成为近年来的研究热点.另一方面,高效蓝光材料的稳定性及色纯度问题一直是该领域研究亟待解决的难题.本文将依据不同电子给受体单元,对电子给体-受体型热活化延迟荧光蓝光材料及其OLED器件的最新进展、发光原理和设计原则进行了简要综述,并对其发展作出展望.     

热活化延迟荧光蓝光小分子取代基效应的研究进展

近年来,作为第三代有机发光二极管(organic light-emitting diodes, OLED)发光材料的热活化延迟荧光(thermally activated delayed fluorescence, TADF)材料受到了学术界和产业界的广泛关注. TADF分子由于其单线态与三线态之间的能级差较小,三线态激子可以被环境热活化而通过反系间窜越上转换至单线态,理论上可实现100%的激子利用率,从而使得OLED器件外量子效率显著提高.TADF材料被认为是突破高效稳定有机电致蓝光发射瓶颈的潜在解决方案.一般, TADF分子为含有电子给体(donor, D)和电子受体(acceptor, A)的纯有机推拉电子体系.通过改变给体单元和受体单元的结构、数量和取代基及其位置可以有效调节TADF分子的单线态-三线态能级差、前线轨道分布、聚集态结构、电致发光颜色及其性能.同时取代基在调控给、受体单元的推拉电子能力及TADF材料的分子构型、聚集态结构和稳定性等物化特性方面扮演着非常重要的角色.本综述分别对D-A型和多重共振型TADF蓝光分子的取代基效应进行了综述,以期为高效稳定的蓝光TADF分...     

带烷氧基的苯基蒎烯吡啶铱配合物的合成及光物理性质

合成了一组新型的带有烷氧基团的铱(Ⅲ)配合物[Ir(RO-pppy)3], 并进行了结构表征. 该组配合物在~496 nm处有较强的三重态发射, 磷光量子产率为0.4~0.6, 三重态寿命为2~4 μs. 结果表明, 连接了长链的配合物可减少分子间的聚集, 可以用作有机电致发光器件中的磷光材料.     

蓝色有机电致磷光主体材料

有机电致发光(OLEDs)因其具有驱动电压低、主动发光、亮度高、视角宽、响应快、耐冲击与震动等特点,在平板显示与照明领域有着广阔的应用前景。磷光有机电致发光二极管(PhOLEDs)由于能够同时利用三重态和单重态激子,内量子效率从理论上可达到100%,从而克服了传统荧光OLEDs只利用单重态激子时效率25%的限制,在过去的几十年里受到业内人士的极大关注。但要实现三重态磷光,通常需要将重金属原子与主体材料进行掺杂,而重金属配合物的磷光寿命相对较长,容易引起浓度猝灭和三重态-三重态湮灭,所以需要找到合适的主体材料与重金属的磷光发射体进行掺杂来减少上述因素的影响从而得到高性能的电致磷光器件。本文综述了近年来国内外蓝色有机电致磷光主体材料的研究状况,并对空穴传输型、电子传输型和双极传输型的蓝色磷光主体材料按照官能团的不同进行了分类总结和评述,并对其光物理性质、热学性质、电化学性质及器件性能等作了详细归纳比较,最后展望了蓝色有机电致磷光主体材料的前景和发展趋势。     

基于磷光材料的电致发光二极管研究进展

电致发光二极管(LEDs)具有能耗低、寿命长、绿色环保等优点,在固态照明、全色显示等领域具有广阔的应用前景。 与传统的荧光电致LEDs相比,磷光电致LEDs能够同时利用单重态和三重态激子,理论上可以使器件的内量子效率达到100%,突破5%的外量子效率极限。 因此,发展高效的磷光材料以及实现其在电致LEDs中的应用是非常有意义的。 本文综述了目前主要的磷光材料,包括有机金属配合物、纯有机分子、聚合物、金属有机框架材料和碳量子点等,并总结了稀有金属配合物和纯有机分子在电致磷光 LEDs中的研究进展,同时对电致磷光LEDs的发展前景进行展望。     

基于给-受体结构的热活化延迟荧光材料

热活化延迟荧光（TADF）材料由于第一单线态（S₁）与三线态激发态（T₁）之间的能级差较小,使得三线态激子能够有效地系间窜越至单线态发光,实现100%的激子利用率,在有机发光二极管（OLED）等领域得到广泛应用,是目前有机电子学研究的热点之一。基于给-受体（D-A）结构构建TADF材料具有分子设计简便、易于制备、性能优异等特点,引起了人们的普遍关注。本文综述了基于D-A结构设计TADF材料的基本原则,依据给受体构筑单元的不同,概括了各类TADF材料的结构和性能特点以及在器件应用等方面的最新研究进展,最后总结了D-A结构型TADF材料尚存在的问题,并对其未来的关键研究方向进行了分析和展望。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.