基于萘二酰亚胺衍生物的给受体共晶的分子自组装和荧光变化

由两种或两种以上不同组分通过π-π相互作用、电荷转移和氢/卤键等非共价相互作用形成的有机共晶体,因其在有机光电子领域中的应用而受到广泛关注.本文通过溶液共结晶的方法制备了三种电荷转移共晶体,以晕苯和芘作为给体,萘二酰亚胺衍生物N,N'-二甲基-1,4,5,8-萘四甲酸二酰亚胺(N,N'-dimethyl-1,4,5,8...     

共晶工程的颜色和形态调控

共晶工程作为化学材料的重要研究手段之一,在光电学、药学等多个领域取得了不同的研究进展与成果。与传统合成方法相比,共晶可通过简便、低成本的操作实现共晶组件的多功能性,同时通过微观调控实现共晶形态、结构乃至颜色的调节。本综述首先介绍了共晶的分类和制备,然后介绍了有机电荷转移共晶发光材料、机械变色发光材料的荧光颜色调控以及药物共晶、有机光电功能共晶的颜色调控;其次,介绍了外部内部因素对晶体形态调控的影响;最后,介绍了共晶晶体多态性和荧光色彩之间的关系以及共晶材料的未来发展。希望本文可以为共晶材料颜色和形态方面的优化与改善提供一定的思路,也为其他化学材料的质量优化提供借鉴意义。     

一种基于有机共晶的光控晶体管

以9,10-二苯乙炔基蒽(BPEA)作为给体分子,均苯四甲酸二酰亚胺(PMD)作为受体分子,通过溶液法制备了一种新型的电荷转移共晶BPEA-PMD.共晶结构中,给受体分子以2:1的摩尔比呈现混合堆积模式.通过一系列的表征,发现了其独特的光电性质,BPEA-PMD共晶分子表现出红色荧光发射特性并且兼具P型传输性能,其空穴...     

有机共晶非线性光学材料及应用研究进展

随着二次谐波(SHG)和双光子吸收(TPA)的产生,有机非线性光学(NLO)材料近十年来在激光频率转换、生物成像、微纳加工、光限幅以及太赫兹波(THz)等领域发挥越来越重要的应用,引起了广泛兴趣.迄今为止,报道的绝大多数有机非线性光学活性材料为单一组分,它们化学合成繁琐、实验条件苛刻且难以打破单一组分固有属性的限制.而复合材料可通过共混、掺杂、共结晶等简易形式迅速地拓宽新材料种类,通过一种分子以上基于分子间非共价相互作用的有机共晶已在很大程度上朝着调节和修改分子固体的物理化学性质的方向发展.然而,目前国内外并没有关于有机共晶在非线性光学领域中的系统性总结与介绍.本综述首先介绍二阶、三阶非线性光学性能参数及其测试方法;接着,介绍共晶材料在该领域的最新研究进展,包括材料的种类、制备方法、产生光学非线性效应的机理等;其次,讨论共晶非线性光学材料潜在的应用;最后,对该领域的发展提供了一些展望,希望能为有机共晶与非线性光学领域的同行研究者们提供一定的借鉴参考.     

光电功能有机晶体研究进展

近几年光电功能有机单晶的研究取得一些重要进展, 是有机光电材料研究领域新的热点. 与无定形材料相比, 有机单晶具有高的稳定性、结构上的有序性、高的载流子迁移率等特性, 在光电器件应用方面具有诸多优势. 单晶具有明确的结构, 为研究有机分子间的基本作用力(超分子作用)、分子的堆积模式等对光电性能(发光、载流子迁移等)的影响提供了一个极好的载体. 通过调控有机晶体中的分子排列, 有机晶体的发光效率已超过80%, 载流子迁移率达10 cm²·V^&;#8722;1·s^&;#8722;1水平, 并在多种晶体中观测到放大受激发射现象. 本文着重介绍光电功能有机单晶的研究进展, 其中涉及一些相关的基本原理介绍.     

聚集诱导发光分子的光电功能与器件应用

光电功能分子通常以薄膜和聚集体的形式显示功能, 聚集诱导发光（AIE）分子体系的发现为解决固态下聚集诱导荧光猝灭（ACQ）难题提供了新的思路. 本文总结了近年来本课题组发展的一系列AIE 分子, 侧重介绍这些AIE 分子的光电功能与器件应用, 特别是在有机电致发光器件和有机激光方面的应用. AIE 材料显示非常高的电致发光效率, 在显示与白光器件方面潜力巨大. 在发展电泵有机激光方面, AIE 材料特点突出, 是最有前景的一类材料.     

基于新型电子受体1,3,5-三苯酰基苯的两种热活化延迟荧光材料的合成及性能研究

以1,3,5-三苯酰基苯（TBP）作为电子受体,1,8-二甲基咔唑（DmCz）和1,3,6,8-四甲基咔唑（TmCz）分别作为电子给体,合成了两种新的热活化延迟荧光材料TBP-DmCz和TBP-TmCz.热重和差热测试结果表明,这两种材料都具有高热稳定性.理论计算显示,材料的最高电子占据轨道和最低电子未占轨道分别分布在咔唑和1,3,5-三苯酰基苯结构单元上,两种分子轨道几乎没有重叠,具有热活化延迟荧光材料分子轨道的典型特征.分子轨道能级测算结果显示,增加咔唑结构单元上甲基的数量,能明显升高材料的最高电子占据轨道能级.TBP-DmCz和TBP-TmCz的最低激发单重态和最低激发三重态间能级差（ΔE_ST）都非常小,分别为0.05和0.01 eV.在甲苯溶液中,两种材料均表现出了明显的分子内电荷转移跃迁吸收,TBP-DmCz和TBP-TmCz的发光峰分别出现在488和502 nm.用TBP-DmCz和TBP-TmCz作为掺杂客体材料制备出了两种高性能电致发光器件,器件的最大外量子效率分别达到了13.6%和18.3%.     

巯基卟啉自组装膜的制备及应用研究进展

详细介绍了巯基卟啉自组装膜的几种制备方法,评述了不同制备方法的优缺点;对卟啉自组装膜在电荷转移、分子氧电催化、分子光电器件等领域的研究进展进行了评述,引用文献54篇。     

苯并噻二唑单元在聚合物光伏材料设计中的应用

聚合物太阳能电池因其易于加工、可制备成柔性器件、材料来源广泛等优点得到材料界和能源界的广泛关注。有机太阳能电池效率的不断提高主要得益于材料的发展和电池器件结构的优化。从材料设计角度考虑,种类众多的给体和受体单元被开发用来构建有机共轭分子,其中,苯并噻二唑单元由于共轭平面较大和吸电子性较强的特性被广泛用于构建高性能的有机太阳能电池材料。基于此,本文首先介绍了苯并二噻吩单元及其衍生物常见的合成方法,随后总结了其在构建聚合物给体方面的应用,最后对其后续发展方向和前景提出了展望。     

可溶液加工的有机-无机杂化钙钛矿:超越光伏应用的“梦幻”材料

有机-无机杂化钙钛矿材料是可通过溶液工艺低温制备得到的直接带隙半导体晶体薄膜.在众多可溶液加工的半导体材料中,有机-无机杂化钙钛矿薄膜是为数不多的低缺陷密度、双极子传输性能优异的晶体薄膜,同时兼具宽光谱吸收和长载流子扩散距离等特性,是平面异质结太阳能电池的理想选择.另外,作为低缺陷密度的直接带隙半导体晶体材料,杂化钙钛矿薄膜具有优异的发光特性.其发光波长可通过能带工程(在分子水平上改变其组分)进行调节,因此有望在发光二极管和激光等光电器件中得到新应用.总结了钙钛矿材料的优异特性和目前应用研究的进展,并对其未来发展做了展望.     

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%.     

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.     

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.     

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.     

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.     

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.