呜拉嗪及其衍生物的合成研究进展

稠环芳烃具有独特的电子性质和光学性质,在有机光电材料领域应用广泛.向稠环芳烃骨架中引入杂原子可改变其电子结构,进而改变其物理、化学、光、电和磁等性质.在众多的杂原子中,氮原子是稠环芳烃中最常见的掺杂原子.呜拉嗪是芘的等电子体,又称吲哚并[6,5,4,3-ija]喹啉,是一种新型氮杂稠环芳烃.近年来,呜拉嗪在染料敏化太阳能电池等领域表现出了潜在应用,随后有关呜拉嗪的合成方法研究备受关注.总结了近年来呜拉嗪及其衍生物的主要合成方法.     

硫杂杯芳烃冠醚的合成及其与氨基酸配合性能的研究

在普通杯芳烃骨架中引入硫原子可以改善普通杯芳烃的配合性能。文中首先合成了硫杂杯[4]芳烃四酰肼衍生物3,在弱酸的催化下继续与化合物4反应,高产率地合成了同时含酰胺和席夫碱单元的硫杂杯[4]芳烃冠醚衍生物5,新化合物的结构经1H NMR、元素分析、ESI-MS等表征证实。同时探讨了新型硫杂杯[4]芳烃衍生物5与系列-α氨基酸的配合性能。     

杯吡咯和杂杯吡咯的结构、合成与应用

杯吡咯以其特殊的结构和优异性能, 在主客体化学尤其是分子识别等方面的应用前景已备受关注, 合成新型功能化杯吡咯及其衍生物已成为超分子化学领域的研究热点之一. 近年来通过引入新型芳烃基体合成了结构和性能多样的杂杯吡咯. 主要介绍了功能化的杯吡咯和杂杯吡咯的结构、合成及其在分子识别等领域的应用.     

硫杂杯[4]芳烃化学修饰的研究进展

硫杂杯[4]芳烃是由S原子取代经典杯芳烃中的桥联亚甲基而成的大环化合物,在分子识别、多核金属配合物、化学传感器等方面有广泛的应用.对硫杂杯[4]芳烃的化学修饰进行综述,有助于新型功能化硫杂杯芳烃衍生物的研究.     

1,4-硼氮杂芳烃在中国的研究进展

稠环芳烃及其衍生物在有机光电材料领域具有广泛应用,杂原子掺杂可有效调节稠环芳烃的物理化学性质.硼氮杂芳烃是稠环芳烃的重要成员.基于硼原子和氮原子的相对位置,硼氮杂芳烃可以分为三种异构体:1,2-硼氮杂芳烃、1,3-硼氮杂芳烃和1,4-硼氮杂芳烃,由于合成上的困难,1,3-硼氮杂芳烃的研究相对较少.近年来,得益于1,4-硼氮杂芳烃在多重共振热活化延迟荧光材料方面潜力的发掘,1,4-硼氮杂芳烃在国内外都取得了飞速发展.我国有机化学及材料化学领域的学者们积极参与并推动了1,4-硼氮杂芳烃的快速发展,在1,4-硼氮杂芳烃的结构开发和应用拓展方面开展了一系列原创性的工作,取得了瞩目的成绩.以1,4-硼氮芳烃的结构作为线索,按照杂原子二元掺杂(B/N)骨架和三元掺杂(X/B/N)骨架分别进行论述,综述了1,4-硼氮杂芳烃的合成发展历史和应用研究拓展,最后对硼氮杂芳烃领域的未来发展与应用进行了展望.     

手性杯芳烃及其超分子手性

杯芳烃是由苯酚单元通过亚甲基连接而成的空腔型分子,具有衍生位点多,构象丰富等特点,被称为第三代主体分子。在分子层次,依手性因素的结构特点不同,可将手性杯芳烃分为具有手性亚单元的杯芳烃、固有手性杯芳烃和桥手性杯芳烃。在超分子层次,杯芳烃自身或杯芳烃与其他分子或离子在溶液中、晶态中或二维表面可通过非共价键力形成多种拓扑结构的纳米手性聚集体。研究手性杯芳烃和基于杯芳烃的超分子手性组装体的合成、结构和性能,不仅在理解手性起源、手性结构等方面具有理论意义,而且有望获得以分子识别为基础的手性传感器、手性催化剂、手性分离材料、手性载体和手性纳米材料。本文综述近十年来有代表性的分子手性杯芳烃和以杯芳烃为组分的超分子手性聚集体的设计、合成、结构和功能。着重展示杯芳烃骨架在形成新颖分子手性和超分子手性上的优势,以及杯芳烃单元在实现特定功能如手性识别时发挥的作用。相信随着杯芳烃合成技术和杯芳烃超分子设计的发展,必将进一步发挥杯芳烃的结构优势,涌现出更多性能优异的手性杯芳烃功能分子和超分子手性杯芳烃功能材料。     

含超微氧化亚钴颗粒Beta分子筛的合成及其催化乙苯氧化性能

杂原子分子筛是指在硅铝分子筛或磷铝酸盐分子筛中含有骨架内或骨架外某种原子或其化合物的分子筛.这些杂原子可以是某些主族元素(如硼、锗、镓)或有变价特性的过渡金属元素(如钛、铁、钴、镍)等.将杂原子或其化合物通过浸渍、离子交换、水热晶化等方式引入沸石分子筛骨架中形成杂原子分子筛,往往可以改变沸石分子筛的骨架结构和理化性能,并赋予沸石分子筛新的催化反应性能.自1983年钛硅分子筛TS-1被发现能够高效催化烯烃环氧化以来,许多杂原子分子筛因其在催化烷烃类及芳烃类氧化、醛酮选择氧化及烯烃类环氧化等领域表现出的优良性能得到了广泛关注.目前,合成含不同杂原子的分子筛已成为分子筛材料开发的一个重要内容.分子筛的微孔孔道结构赋予了被引入其中作为催化中心的杂原子对反应物/产物分子独特的择形选择性;同时,分子筛骨架与杂原子之间往往存在化学键或空间限域作用,使得杂原子在高温高压等反应条件下依然保持高度的分散性,避免由于团聚导致活性降低.钴离子及含钴化合物在烷烃及芳烃类催化氧化反应中表现出很好的活性,能够利用分子氧实现对高碳烷烃及烷基苯的催化氧化.将钴离子及其化合物引入具有合适孔道结构的分子筛,可以提高催化反应的选择性.目前将对含钴分子筛的合成研究主要有后处理法及直接水热法.后处理法包括负载法及离子交换法,用于制备含有钴物种的硅铝分子筛;而直接水热法主要用于制备含有骨架钴的磷酸铝分子筛.目前为止,使用水热法合成含钴的分子筛材料的合成及其催化应用至今鲜有研究报导.这主要是由于传统的分子筛合成体系的高碱性环境会导致钴盐的沉淀,导致其无法被引入分子筛.我们通过优化合成条件,利用含氟体系直接水热法将钴引入Beta分子筛,得到含超微氧化亚钴团簇的Beta沸石分子筛.通过扫描电子显微镜、X射线粉末衍射、紫外-可见漫反射光谱、X射线光电子能谱、透射电子显微镜及H2程序升温还原等表征手段对合成样品的物理化学性质进行了研究,并与使用浸渍、离子交换得到的含钴Beta沸石及水热合成得到的含钴AlPO-5分子筛的相关性质进行了对比.合成得到的含钴分子筛材料中,钴物种以亚纳米尺度的氧化亚钴颗粒形式存在.我们使用分子氧作为氧源,考察了该含超微氧化亚钴的Beta沸石作为催化剂催化乙苯氧化反应的活性.与浸渍、离子交换制得钴硅分子筛及含有骨架钴的磷酸铝分子筛材料相比,含超微氧化亚钴的Beta分子筛表现出更高的催化活性及对苯乙酮/醛的选择性.     

下缘含有杂原子杯[4]芳烃的合成 及其阳离子选择性

合成了一系列下缘含有杂原子的杯芳烃衍生物, 其晶体结构和核磁研究证实杯芳烃以锥式构象存在, 并且通过溶剂萃取法研究了它们对过渡金属和重金属的阳离子键合能力和选择性. 实验结果表明: 将氮、硫、磷等杂原子引入杯芳烃的下缘可以提高其对银、铅等重金属的萃取能力.     

含超微氧化亚钴颗粒Beta分子筛的合成及其催化乙苯氧化性能（英文）

杂原子分子筛是指在硅铝分子筛或磷铝酸盐分子筛中含有骨架内或骨架外某种原子或其化合物的分子筛.这些杂原子可以是某些主族元素(如硼、锗、镓)或有变价特性的过渡金属元素(如钛、铁、钴、镍)等.将杂原子或其化合物通过浸渍、离子交换、水热晶化等方式引入沸石分子筛骨架中形成杂原子分子筛,往往可以改变沸石分子筛的骨架结构和理化性能,并赋予沸石分子筛新的催化反应性能.自1983年钛硅分子筛TS-1被发现能够高效催化烯烃环氧化以来,许多杂原子分子筛因其在催化烷烃类及芳烃类氧化、醛酮选择氧化及烯烃类环氧化等领域表现出的优良性能得到了广泛关注.目前,合成含不同杂原子的分子筛已成为分子筛材料开发的一个重要内容.分子筛的微孔孔道结构赋予了被引入其中作为催化中心的杂原子对反应物/产物分子独特的择形选择性;同时,分子筛骨架与杂原子之间往往存在化学键或空间限域作用,使得杂原子在高温高压等反应条件下依然保持高度的分散性,避免由于团聚导致活性降低.钴离子及含钴化合物在烷烃及芳烃类催化氧化反应中表现出很好的活性,能够利用分子氧实现对高碳烷烃及烷基苯的催化氧化.将钴离子及其化合物引入具有合适孔道结构的分子筛,可以提高催化反应的选择性.目前将对含钴分子筛的合成研究主要有后处理法及直接水热法.后处理法包括负载法及离子交换法,用于制备含有钴物种的硅铝分子筛;而直接水热法主要用于制备含有骨架钴的磷酸铝分子筛.目前为止,使用水热法合成含钴的分子筛材料的合成及其催化应用至今鲜有研究报导.这主要是由于传统的分子筛合成体系的高碱性环境会导致钴盐的沉淀,导致其无法被引入分子筛.我们通过优化合成条件,利用含氟体系直接水热法将钴引入Beta分子筛,得到含超微氧化亚钴团簇的Beta沸石分子筛.通过扫描电子显微镜、X射线粉末衍射、紫外-可见漫反射光谱、X射线光电子能谱、透射电子显微镜及H_2程序升温还原等表征手段对合成样品的物理化学性质进行了研究,并与使用浸渍、离子交换得到的含钴Beta沸石及水热合成得到的含钴AlPO-5分子筛的相关性质进行了对比.合成得到的含钴分子筛材料中,钴物种以亚纳米尺度的氧化亚钴颗粒形式存在.我们使用分子氧作为氧源,考察了该含超微氧化亚钴的Beta沸石作为催化剂催化乙苯氧化反应的活性.与浸渍、离子交换制得钴硅分子筛及含有骨架钴的磷酸铝分子筛材料相比,含超微氧化亚钴的Beta分子筛表现出更高的催化活性及对苯乙酮/醛的选择性.     

基于硼氮杂稠环芳烃的多重共振热活化延迟荧光材料研究进展

近年来,多重共振热活化延迟荧光(multi-resonance thermally activated delayed fluorescence, MR-TADF)材料由于其优异的光物理性质和电致发光器件性能而受到广泛关注.这类材料通常以稠环芳烃骨架为基础,通过引入具有相反共振效应的缺电子中心(如硼原子)和富电子中心(如氮原子),诱导最高占据分子轨道(HOMO)和最低未占分子轨道(LUMO)在分子骨架中分别定域在不同原子上,从而获得小的单线态-三线态能级差(ΔEST),实现TADF的性质.与传统的给受体型TADF材料相比, MR-TADF材料具有刚性结构和局域电荷转移特征,有利于获得高色纯度的窄谱带发光和极高的量子效率,使其成为理想的发光材料并广泛应用于有机发光二极管(organiclight-emittingdiode,OLED)中.自2016年首例基于硼氮杂稠环芳烃的MR-TADF材料被报道以来,该领域取得了飞速的发展,但尚缺乏针对材料分子研究进展的系统总结.综述了基于硼氮杂稠环芳烃的MR-TADF分子的设计策略和合成方法,从分子骨架的发展、分子骨架的取代基修饰策略以及新型手性MR...     

Effect of covalent functionalization of C60 fullerene on its encapsulation by water soluble calixarenes

The molecular encapsulation of functionalized fullerenes (substituted fulleropyrrolidines) with water-soluble calixarenes was studied by photoluminescence and quantum-chemical methods. The results show that both the thiacalix[4]arene-tetrasulfonate and calix[6]arene-hexasulfonate are able to overcome the natural water-repulsive character of fullerenes. However, the functionalization of calixarenes and fullerenes induces significant changes in the molecular encapsulation processes, and the obtained thermodynamic behavior of the complex formation highlights the importance of the entropy. Our results can contribute to the development of the synthesis and design of functionalized calixarenes supporting their application in pharmaceutical and food chemistry.     

Electronic parameters of cation complexation by calixarene ionophores

The Gibbs energy of extraction experiments of ionophoric calixarenes with alkali metals from the literature have been correlated with electronic parameters of their “monomeric” structures calculated by AM1, PM3 and PM7 algorithms: energies of molecular orbitals and charge densities of oxygen and nitrogen atoms. We observed general correlations of the extraction constants with the charge on the carbonyl oxygen and specific correlations with MO-energy using the covalent term of the Klopman–Salem equation. The correlations for calixarenes with 5 and 6 phenolic units were very poor, and we attributed to the structural flexibility, which allow different optimized conformations for metal binding.     

Calixarenes for Biochemical Recognition and Separation

This review summarizes reference data on the molecular recognition of bioactive molecules by calixarenes. It emphasizes on selectivity, the design principles of the host molecules, and the type of interactions as basis for new analytical and separation methods. The following classes of compounds are discussed: amino acids, peptides and proteins, lectins, enzymes, nucleotides and nucleosides, saccharides, steroids and other guests. Also considered are induced chirality and calixarenes with substituents complementary to biomolecules. Enzyme mimics and amines are briefly discussed.     

杯芳烃在液相色谱、毛细管电泳和电色谱中的应用进展

利用杯芳烃的分子识别作用提高色谱分离选择性是超分子化学在分离科学中的成功应用.本文从杯芳烃分离材料的制备、分离机理和应用等,综述了近年来杯芳烃在液相色谱、毛细管电泳和电色谱中的研究进展.     

Properties of amorphous and crystallizable hydrocarbon polymers. III. Studies of the hydrogenation of polybutadiene

Three methods for hydrogenating anionically prepared polybutadiene (containing about 8% vinyl double bonds) were investigated: homogeneous catalysis (alkylated transition metal salts), heterogeneous catalysis (nickel on kieselguhr; paladium on calcium carbonate), and stoichiometric reaction with in situ generated diimide. The products were characterized by intrinsic viscosity, gel permeation chromatography, infrared spectroscopy, and melt viscosity. Only the heterogeneous catalysts were found to yield completely hydrogenated products without incorporation of foreign groups and without significant change in the large-scale molecular structure of the chain. The 195°C melt viscosity of linear polybutadiene hydrogenated with heterogeneous catalysts is virtually identical with that of linear polyethylene with the same intrinsic viscosity in trichlorobenzene at 135°C. The solid state properties of hydrogenated polybutadiene, containing about 20 ethyl branches/1000 main chain atoms, closely resemble those of commercial branched polyethylene.     

Quantum‐chemical approach to the solvatochromic transition in polysilane derivatives

We approached the solvatochromic transition observed in polysilane derivatives (poly[bis(4‐propoxybutyl)silylene] (PPBS)) from the standpoint of various quantum chemical treatments. It was found from conventional geometry optimizations at the levels of semiempirical and ab initio molecular orbital methods that a protonation to polysilane oligomers with side chain R = ? OCH₃ results in the conformational change of Si‐backbone to a trans‐zigzag structure. Using the Elongation method, which was developed for efficient calculations of huge systems, it was demonstrated that a protonation could change the conformation of Si‐backbone to a trans‐zigzag structure over 10–14 Si atoms. In addition, ab initio calculations showed that the positive charge of a proton can delocalize into the Si‐backbone through a long side chain in PPBS. Positively charged polysilane oligomers provide a rotational barrier that prefers a trans‐zigzag structure, whereas neutral oligomers have a barrier that results to a random structure. This unique behavior of the charged polysilane oligomers should not be disregarded in understanding the mechanism of the solvatochromic transition in PPBS. In ab initio configuration interaction/Mφller‐Plesset through‐space/bond interaction analysis, it was found that such a unique behavior of the rotational barrier in polysilane oligomers could be explained by the effect of orbital delocalization through σ‐conjugation on the Si‐backbone. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 119–133, 2006     

Heterocalixaromatics, new generation macrocyclic host molecules in supramolecular chemistry

Heterocalixaromatics, the heteroatom bridged calix(hetero)arenes, have been emerging as new generation macrocyclic host molecules in supramolecular chemistry recently. Being different from the conventional calixarenes in which the aromatic rings are linked by methylene units, heterocalixaromatics assemble various aromatic rings by different heteroatoms. Owning to the intrinsic nature of heteroatoms that can adopt different electronic configurations to form various degrees of conjugation with their neighboring aromatic rings, heterocalixaromatics exhibit unique structural features and versatile recognition properties in comparison to conventional calixarenes. This feature article highlights recent advances in the synthesis, functionalization, structure and molecular recognition of nitrogen- and/or oxygen-bridged calixaromatics, with a primary focus on our own work.     

Calixarenes and related macrocycles as gene delivery vehicles

The success of gene therapy depends largely on the development of new efficient gene delivery vehicles. The emerging class of molecules for this application is macrocycles that feature persistent shape, thus ensuring higher level of supramolecular organization of the DNA complexes. The review focuses on recently developed calixarenes and close analogues as gene delivery vectors, their chemistry, ability to compact nucleic acids, transfection ability in vitro and cytotoxicity. Their fixed conformation with the possibility of multiple functional groups at the upper and lower rims allows preparation of cone-shaped macromolecules capable of programmed hierarchical assembly in the presence of DNA. It is shown that specially designed calixarenes, particularly those having amphiphilic structure with clustered DNA binding units, can form small virus-sized DNA nanoparticles with well-defined architecture, high transfection efficiency and low toxicity. The field is still largely underexplored so that there is a lot of room for further improvement of the molecular design of calixarenes. Moreover, their evaluation in vivo on animals will be an important step towards their validation for gene therapy.     

一种结合均相和非均相催化剂优势的聚乙炔纳米颗粒负载的钯（II）催化剂

负载型的金属催化剂虽然分离方便,但在反应活性、选择性以及催化剂的结构表征方面均明显不如相应的均相催化剂。将均相催化剂通过不同的化学键固载于高比表面积载体是实现均相催化剂多相化的重要途径,这样可使催化剂兼具均相和多相催化剂的优势。然而要将均相催化剂锚定于特定载体上,通常涉及较为复杂的合成反应,对载体也有严格的要求。因而该法仅仅适用于实验室研究,难以实现规模生产。因此,提供一种简便有效地制备兼具均相和多相催化剂优势的催化剂合成方法非常必要。本文报道一种简便的制备聚乙炔纳米颗粒负载Pd(II)催化剂(NP-Pd(II))的方法,所制催化剂在水相中的Suzuki-Miyaura偶联反应中表现出极高的活性,同时具有便于分离、容易放大制备的特点。在室温下,将乙炔气通入PdCl42-的水溶液中迅速变得浑浊,静置后容器底部有棕色沉淀,同时溶液变为无色透明。固体产物使用水、乙醇等溶剂进行洗涤;干燥之后收集既得聚乙炔纳米颗粒负载的Pd(II)催化剂NP-Pd(II)。使用透射电子显微镜、红外(IR)及拉曼吸收光谱、X射线衍射(XRD)、X射线光电子能谱(XPS)以及X射线吸收光谱(EXAFS)等手段对NP-Pd(II)进行了详细表征。结果显示,在NP-Pd(II)中Pd并非以Pd纳米颗粒形式存在; XRD中没有未Pd纳米晶的特征衍射峰。 IR等表征证明乙炔在Pd的催化作用下发生聚合作用,生成了聚乙炔。 EXAFS结果表明, Pd分别和氯原子以及C=C双键进行配位;同时,没有观察到Pd–Pd键的生成,进一步证明了Pd未被还原为Pd纳米颗粒。 XPS也印证了Pd(II)的价态。形貌上, NP-Pd(II)为直径2–3nm的颗粒,其中的Pd原子均匀分散于聚乙炔纳米颗粒上,使其在反应过程中能够充分地与底物接触,从而在Suzuki-Miyaura偶联反应中表现出极高的活性。更重要的是,由于“憎水效应”, NP-Pd(II)在溶液中以微米级的聚集体形式存在,因而反应后通过离心或者静置从反应体系中分离出来。因此,在NP-Pd(II)催化剂中,每个Pd原子都是潜在的活性中心,这与典型的均相催化剂相似;同时,其独特的形貌使其具备了多相催化剂便于分离的特点。因此, NP-Pd(II)是一种兼具均相和多相催化剂优点的催化剂且其催化剂的制备方法极为简便。乙炔是常用的工业气体,溶剂采用水,制备在室温下即可完成,我们也成功地制备出克级规模的高活性、稳定性的NP-Pd(II)催化剂。     

Selenium-containing core-expanded naphthalene diimides for high performance n-type organic semiconductors

The incorporation of heavy atoms into molecular backbone is an extremely straightforward strategy for fine-tuning the optoelectronic properties of organic semiconductors. However, it is rarely studied in n-type small molecules. Herein, by selenium substitution of NDI3 HU-DTYM2, two Se-decorated core-expanded naphthalene diimides(NDI) derivatives DTYM-NDI3 HUDSYM(1) and NDI3 HU-DSYM2(2) were synthesized. In comparison with the reference S-containing compound NDI3 HUDTYM2, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) energy levels of 1 and 2 were fine-tuned with ?HOMO of about 0.2 e V, ?LUMO of 0.1 e V and the narrowed HOMO-LUMO gaps. More surprisingly, the as-spun organic thin film transistors(OTFTs) based on 1 and 2 both showed μe,satvalues as high as1.0 cm~2 V~(-1) s~(-1), which are 2-fold higher than that of NDI3 HU-DTYM2 with the same device structure and measurement conditions. In addition, the single crystal OFET devices based on Se-containing compound NDI2 BO-DSYM2 showed a highμe,satvalue of 1.30 cm~2 V~(-1) s~(-1). The molecular packing of NDI2 BO-DSYM2 in single crystals(two-dimensional supramolecular structure formed by intermolecular Se···Se interactions) is quite different from that of a S-containing compound NDI-DTYM2(one dimensional supramolecular structure formed by intermolecular π-π stacking). Therefore, the Se substitution can cause dramatic change about molecular stacking model, giving rise to high n-type OTFT performance. Our results demonstrated an effective strategy of the heavy atom effect for designing novel organic semiconductors.