基于芘并咪唑的电致发光材料的合成与表征

以芘和咪唑为基本构筑单元,利用"一锅法"合成了一系列芘并咪唑衍生物PyPI,PyTPAI,PyCzI和Pyd-CzI.采用质谱、核磁和元素分析等手段表征了化合物的结构.通过调节与芘并咪唑相连接的共轭基团的种类、大小和空间构型,实现对分子热学性质,分子轨道能级和光电性质的调控.进一步制备了有机电致发光器件,得到了较好的器件性能.     

基于N,C螯合π共轭骨架的四配位有机硼化合物及其光电应用

具有N,C-螯合π共轭骨架的四配位有机硼化合物,其分子内存在的B-N配位作用使分子骨架趋于平面,π共轭性增强,使这类化合物具有较高的电化学和热学稳定性、优异的发光性能和强的电子亲和势,成为非常有发展前景的新型光电材料,已在有机发光二极管(OLEDs)、有机场效应晶体管(OTFTs)、有机太阳能电池、传感等方面进行了广泛研究。在本文中,我们主要介绍了N,C-螯合四配位有机硼化合物的合成方法及其在电子传输材料、发光材料、光致变色材料及有机太阳能电池材料中的应用研究。     

含偶氮苯的双金属钌配合物的合成及性质研究

近几十年来,光致变色在实际中的应用日益增多,特别是有机发光材料在光信息存储、分子开关和其他的光学器件方面,有着广泛的发展前景并且已经取得了许多突出成就,引起了广泛的关注[1].而有机偶氮化合物在光作用前后,其化学结构能够发生改变,因此在光开关和高精密度的信息存储材料方面得到了很好的应用.将金属原子引入到具有光致变色性质的偶氮化合物中,特别是那些具有空d轨道的过渡金属和空f轨道的稀土金属.由于他们的价电子数变化多,并且分子结构特殊,材料性能可以在很大的范围内进行调变.同时这些金属配合物分子中大多都具有共轭的π键,可以发生分子内电子转移反应,引起价电荷的转移,因而这一类化合物在光电功能材料方面具有很大的发展前景[2].     

带有噻吩侧基的有机硼小分子电子受体光伏材料

有机小分子电子受体材料的侧基能够影响异质结有机太阳能电池的给体/受体匹配和器件性能。我们设计并合成了一个硼原子带有噻吩侧基的有机硼小分子(MBN-Th)。该分子的LUMO离域在整个骨架上,HOMO定域在中心核上,其独特的电子结构使该分子具有两个强的吸收峰(波长分别为490和726nm),因此分子具有宽的吸收光谱和强的太阳光吸收能力。与苯基侧基相比,噻吩侧基使分子的HOMO能级下移0.1 eV,LUMO能级保持不变,进而引起分子带隙减小和吸收光谱蓝移20nm。基于该有机硼小分子受体材料的异质结有机太阳能电池,实现了4.21%的能量转化效率和300–850nm的宽响应光谱。实验结果表明,硼原子上的噻吩侧基是调控有机硼小分子光电性质的有效方法,可以用于有机硼小分子受体材料的设计。     

有机硼π-共轭光电功能材料*

由于硼元素所特有的一些性质,如硼原子空的p轨道与π-共轭体系的π^*轨道间的p_π-π^*共轭效应与Lewis碱络合所表现出的强Lewis酸性以及为获得足够的动力学稳定性在硼原子上所引入的大体积芳香取代基使之表现出的立体位阻效应等,将硼引入到π-共轭体可以赋予体系一些独特的光电性能,因此近年来含硼元素的π-共轭材料引起了人们极大的研究兴趣。这类材料已经显示出非常广阔的潜在应用前景,可以用作非线性光学材料、双光子吸收和发光材料、有机电致发光器件中的电子传输材料和发光材料以及化学传感器等。本文根据π-共轭体系分子结构的不同,对有机硼π-共轭材料,包括硼取代基位于末端的线形π-共轭体系、硼原子位于中心的星形π-共轭体系、硼原子位于主链的π-共轭聚合物体系、硼原子桥联的并环π-共轭体系以及硼取代基位于侧链的π-共轭体系等的研究进展进行了综述,并对该领域的发展前景进行了展望。     

基于N,C螯合π共轭骨架的四配位有机硼化合物及其光电应用

具有N,C-螯合π共轭骨架的四配位有机硼化合物,其分子内存在的B-N配位作用使分子骨架趋于平面,π共轭性增强,使这类化合物具有较高的电化学和热学稳定性、优异的发光性能和强的电子亲和势,成为非常有发展前景的新型光电材料,已在有机发光二极管（OLEDs）、有机场效应晶体管（OTFTs）、有机太阳能电池、传感等方面进行了广泛研究。在本文中,我们主要介绍了N,C-螯合四配位有机硼化合物的合成方法及其在电子传输材料、发光材料、光致变色材料及有机太阳能电池材料中的应用研究。     

以主族元素为桥的梯形化合物的光电性质

梯形化合物具有大的平面π共轭结构, 不会产生构象扭曲, 可以有效增加π共轭长度, 因而表现出非常好的光电性质. 将主族元素引入到梯形化合物骨架中作为桥接单元不仅可以固定其结构而且由于主族元素和π共轭骨架之间的轨道相互作用, 可以实现对这类化合物光电性质的调节. 采用密度泛函理论对一系列主族元素桥的梯形化合物的结构和光电性质进行了理论研究, 从而可更好地理解和预测这类化合物的性质. 研究发现, 这类化合物的电子结构可以通过引入主族元素进行调节. 由于具有更大的π共轭程度, 四主族元素桥化合物的吸收与双主族元素桥化合物相比有明显的红移, 而且荧光寿命较短. 另外, 通过计算离子化势(IPs)、电子亲和能(EAs)和重组能(λ)考察了这类化合物的电子和空穴注入及传输性质. 研究发现, 四主族元素桥化合物表现出更强的电子和空穴注入能力.     

8-氨基喹啉骨架螯合的四配位B,B-二芳基络合物的合成与计算研究（英文）

尽管四配位有机硼配合物作为荧光材料已被广泛应用,但硼中心上连接有两个芳基的配合物的合成方法仍然较少.该类化合物的合成一般需要使用敏感的有机金属试剂.本工作使用市售可得、化学稳定的芳基三氟硼酸钾盐作为二芳基硼结构的来源,以8-氨基喹啉作为螯合配体,以中等至优异的产率获得了一系列先前难以制备的二芳基硼络合物.此外,对所得配合物的密度泛函理论计算研究揭示了其分子轨道分布.     

从单分子到分子聚集态科学

有机光电功能材料的宏观性能不仅只依赖于基元分子自身的理化性质,还取决于其分子聚集行为和聚集态结构。在特定的聚集态结构中,分子间弱相互作用的加和与协同,可促进体系性能的拓展与质变,获得超越分子本征属性的功能。这凸显出当前化学研究逐步从关注单分子向分子聚集态科学转变,体现出分子聚集态研究的重要性。本文借助有机室温磷光性能对分子聚集态结构的高度灵敏性与响应性,系统探讨了分子聚集态结构的形成规律与核心影响因素。以此为基础,进一步拓展分子聚集态研究的应用领域,包括力致发光、有机二阶非线性光学、力致变色、有机发光二极管等,从静态调控到动态刺激响应(刺激源:力、热、光、电场等),从单一结构到多组分体系与器件,同时,确立了各种有机光功能材料的优势分子聚集形式,提出了聚集态调控的有效策略与研究思路,阐述了光电功能材料体系设计与合成的可控性与预见性。     

卟啉类化合物分子光电器件研究进展

分子电子器件是未来分子电路的微电子元件,已成为有机功能纳米材料研究的热点。 卟啉类化合物的π共轭体系表现出的独特光电性能和良好的热稳定性,使其作为光电器件、模拟生物酶、分子识别和传感材料在材料化学、医学、生物化学和分析化学等领域展现出良好的应用前景,由于卟啉分子平面结构的易修饰性,常用卟啉化合物组装单元来构建功能化的卟啉光电器件。 本文综述了卟啉类化合物的特点及其在光电器件中的应用进展。     

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%.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.