联萘基手性发光材料的圆偏振发光

本文综述了近年来基于联萘基结构的圆偏振发光材料的研究工作.从光致发光和电致发光两方面总结了不同体系下联萘基材料的圆偏振发光,为相关领域的研究者提供了设计思路,并对圆偏振发光材料的研究发展方向进行了展望.     

手性有机小分子圆偏振发光的研究进展

圆偏振发光不仅能直观地反映手性发光体系的激发态结构信息,而且在3D显示、自旋信息通讯、信息存储与处理、CPL激光、生物探针等领域具有广泛的应用前景.因此,近年来圆偏振发光材料引起了人们越来越多的兴趣与关注,成为有机发光功能材料领域一个新的研究热点.本综述总结近年来关于手性有机小分子圆偏振发光的研究进展,主要围绕具有中心手性、轴手性、面手性和螺旋手性的圆偏振发光有机小分子展开介绍.     

圆偏振热活化延迟荧光材料及其器件的研究进展

圆偏振热活化延迟荧光材料具有分子结构易修饰、激子利用率高及圆偏振发光等特点,在光学信息存储、3D显示、发光器件和数据加密等领域具有广阔应用前景.利用此类材料作为发光层制备的圆偏振有机发光二极管,能够同时实现高发光不对称因子和理论上达100%的激子利用率,对发展低功耗和高性能有机发光二极管至关重要.近年来,通过不断的分子结构设计与优化,该类材料在有机发光二极管中的电致发光效率不断提高,但是仍然存在不对称因子低及效率滚降严重等问题.基于此,整理了目前已报道的圆偏振热活化延迟荧光化合物,重点讨论了其分子结构设计与光物理性质、圆偏振特性以及电致发光性能的关系规律,并对高性能圆偏振热活化延迟荧光材料的制备及其在有机发光二极管中的应用进行了展望.     

超分子组装体激发态手性的响应性

圆偏振发光主要是指手性发光体系激发态的性质。由于其在信息加密、高分辨3D显示和智能传感器等领域的潜在应用而备受关注。圆偏振光除了可以通过物理方法获得,即使用线偏振片和四分之一波片的组合,还可以直接从具有光致发光或电致发光性质的手性材料中获得。目前研究者们已经开发了多种圆偏振发光材料,主要包括手性有机分子、手性金属配合物等小分子发光体系以及手性超分子组装体等复合体系。通过将手性组分与响应性功能基团结合而构筑的响应性自组装发光体系对实现智能圆偏振发光材料的发展起着重要作用。在这篇文章里,我们对手性超分子自组装发光体系对各种外界刺激的响应性能进行了总结和归纳,如光照、pH值、溶剂、温度、金属离子等。本综述通过对各种外部刺激对手性组装体激发态性能影响的总结和讨论,旨在进一步推动智能圆偏振发光材料在多学科领域的应用。     

基于八氢联萘酚的大位阻手性发光材料构建及光电性质研究

以手性发光材料为发光中心制备能够直接发射出圆偏振电致发光(circularly polarized electroluminescence, CPEL)的器件, 即CP-organic light-emitting diode (CP-OLED), 在3D显示领域有极大的应用前景. 本工作设计了基于八氢联萘酚的手性热激活延迟荧光材料(S/R)-OBN-tBuCz, 八氢联萘酚作为有效的手性源, 而叔丁基咔唑取代的氰基苯作为高效发光部分. 八氢联萘酚外围较多的氢原子以及较大的叔丁基可以有效增加手性发光分子的空间位阻, 降低堆积效应, 抑制浓度淬灭, 有效提升器件的发光效率. 所合成的手性发光材料展现出明亮的绿光发射(523 nm)、高的荧光量子产率(85.2%)、较小的单线态-三线态能级差ΔE_ST (0.05 eV)和优秀的热稳定性. 圆二色(CD)与圆偏振发光(CPL)光谱显示出明显的对称圆偏振发光信号, 且溶液中的g_PL为+8.6×10^-4和–6.5×10^-4. 基于(S/R)-OBN-tBuCz的电致发光器件表现出优异性能: 起亮电压为3.9 V, 最大亮度为27709 cd•m^-2, 最大电流效率为43.8 cd•A^-1, 最大功率效率为33.5 lm•W^-1, 最大外量子效率为12.4%, 效率滚降很低, 并显示出明显的圆偏振电致发光信号, g_EL分别为+1.57×10^-3和–0.90×10^-3. 大位阻手性发光材料的设计有助于实现高效的CP-OLED, 该研究能促进手性发光材料及圆偏振电致发光器件等相关研究领域的发展.     

圆偏振发光性质的热活化延迟荧光材料及电致发光器件

具有圆偏振发光性质的热活化延迟荧光(circularly polarized thermally activated delayed fluorescence,CP-TADF)材料,因其在数据存储、生物成像以及3D显示等领域的应用前景,受到学者们的广泛关注。基于此类材料所制备的圆偏振热活化延迟荧光器件展现出优异的器件性能。本文从圆偏振热活化延迟荧光材料的发光机理及分子设计策略出发,依据CP-TADF材料构筑方法的不同,概括了其结构设计策略,系统地综述了各种类型CP-TADF材料的分子结构和光电性能的关系及其在电致发光器件领域的应用,最后探讨了目前CP-TADF材料存在的问题,并展望了其未来发展前景及挑战。     

稀土高分子发光材料研究的新进展

介绍了稀土高分子发光材料的发光机理及其发展历程，对其合成方法以及研究方向进行了综述，着重阐述了掺杂型和键合型稀土高分子发光材料研究的最新进展，并对其发展方向和应用前景作了展望。     

推拉电子结构手性四配位硼的光学性质

圆偏振发光(Circularly polarized luminescence,CPL)有机分子是一类重要的手性光学材料,在有机光学和有机电子学等领域受到广泛关注。通过引入手性联萘基团和构建推拉电子结构的设计理念同时实施到双硼氮桥联联吡啶单元,发展出了一系列具有推拉电子结构的手性四配位硼分子。结果表明,改变给电子单元可以调节分子的发光现象,含有二苯胺(2a)和咔唑(2b)单元的分子展现出典型的聚集诱导荧光淬灭现象,而含有9,9-二甲基-9,10-二氢吖啶(2c)单元的分子具有特征的聚集诱导发光性质。手性联萘基团的引入使3个分子具有手性光学性质,展现出圆二色信号和圆偏振发光特性,它们的不对称因子均超过了1×10^-3,另外,改变给电子单元有效调节了手性分子的发光颜色。     

基于手性环己二胺稀土Eu(Ⅲ)高分子在能量传递和圆偏振荧光调控方面的研究

手性(R,R)-1,2-环己二胺分别与具有偶数亚甲基烷烃链的S-M-1(4,4'-(butane-1,4-diylbis(oxy))-dibenzaldehyde),S-M-2(4,4'-(octane-1,8-diylbis(oxy))dibenzaldehyde)和S-M-3(4,4'-(dodecane-1,12-diylbis(oxy))-dibenzaldehyde)单元,通过亲核取代-消除反应合成相应的新颖柔性高分子P-1,P-2和P-3.Eu(TTA)3·2H2O分别与P-1,P-2和P-3反应制备相应的柔性稀土Eu(Ⅲ)高分子P-4,P-5和P-6.通过对烷烃主链数目的有效调控,能够有效调控稀土Eu(Ⅲ)的发光效率和圆偏振荧光的不对称因子(glum).实验证明,在一定的激发状态下,稀土高分子仅仅显示Eu(Ⅲ)的红色特征荧光,归于高分子将激发态能量基本传递给配位中心的Eu(Ⅲ)离子.通过对稀土Eu(Ⅲ)高分子的荧光寿命和量子效率表征,P-4,P-5和P-6的发光效率依次降低.P-4与P-5圆偏振荧光(CPL)的最大不对称因子(glum)分别为+0.0873和+0.0115,归属为电偶极跃迁(5D0→7F2);P-6最大不对称因子(glum)为+0.0539,归属为磁偶极跃迁(5D0→7F1).通过烷烃主链数目的差异实现对其CPL的有效调控,调控机理归于高分子折叠所引起稀土Eu(Ⅲ)不对称配位环境的变化.     

有机偏振发光材料及其成膜技术研究进展

本文对近年来有机偏振发光及其发光材料和成膜技术的发展进行了综述。重点从材料化学结构与偏振发光的关系出发,系统地讨论了几类发光材料的性质、定向排列成膜的方法及其有机偏振发光器件的制作和应用。     

CIRCULAR POLARIZATION OF FLUORESCENCE EMITTED BY AN OPTICALLY ACTIVE COMPOUND

C hiral compounds absorb circularly polarized light of opposite sense to different extents. This property, commonly known as circular dichroism, CD, is closely related to the optical rotatory dispersion of the compound under study, and has been extensively applied to the study of chiral compounds[1, 2]. On the other hand, very little information is available concerning the preferential emission of circularly polarized light of one sense over that of the opposite sense from chiral luminescent compounds. The scarcity of data about circularly polarized luminescence, CPL, is probably due to lack of suitable instrumentation for the measurement of small amounts of circularly polarized light present in a large background of unpolarized luminescence. Indeed, the only CPL data available are of a few substances which exhibit an exceptionally high degree of circular polarization in their emitted light [3, 4].     

Photochemistry with Circularly Polarized Light

The reactions induced by circularly polarized light are reviewed and a general discussion of the induction of optical activity by circularly polarized light is presented. It is concluded that three different mechanisms, or their combinations, can cause asymmetric induction. In each case the optical yield is dependent on the optical anisotropy factor g, the ratio between the circular dichroism (Δ?) and the extinction coefficient (?). The results are discussed in terms of the presumed mechanisms, and particular attention is paid to the asymmetric synthesis of helicenes. It is concluded that this kind of photochemistry may have analytical importance.     

Chiral Ligand-Driven Systematic Synthesis of Coordination Polymers with Non-centrosymmetric Structures

Chirality is an important concept in chemistry revealing intriguing optical properties such as circular dichroism (CD), circularly polarized luminescence (CPL), etc. As one of the non-centrosymmetric (NCS) classes, chiral materials with extended structures may exhibit unique nonlinear optical (NLO) properties, such as second-harmonic generation (SHG). In this Concept article, a series of recently discovered NCS coordination polymers (CPs) from use of carefully designed chiral organic ligands are reviewed. Combining several metal cations such as lanthanides, lead, zinc, and cadmium with rigid chiral ligands has resulted in interesting CPs with both polar and nonpolar structures. Detailed structures, SHG properties, and structure-property relationships are provided. The importance of hyperpolarizability formed by intermolecular hydrogen boding interactions to SHG is emphasized.     

Fmoc-protected amino acids as luminescent and circularly polarized luminescence materials based on charge transfer interaction

Fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids are effective building blocks in self-assembled architectures at hierarchical levels, which however show limited luminescent properties and chiroptical activities. Here we introduce a charge-transfer strategy to build two-component luminescent materials with emerged circularly polarized luminescence properties. A library of Fmoc-amino acids was built, which selectively form charge-transfer complexes with the electron-deficient acceptor. Embedding in amorphous polymer matrix or physical grinding could trigger the charge-transfer luminescence with adjusted wavelengths in a general manner. X-ray diffraction results suggest the multiple binding modes between donor and acceptor. And, the solution-processed coassembly could selectively exhibit circularly polarized luminescence with high dissymmetry g-factors. This work illustrates a noncovalent charge-transfer strategy to construct luminescent and chiroptical organic composites based on the easy-accessible and economic chiral N-terminal aromatic amino acids.     

光学活性金属卟啉的磁手性效应研究

磁光学活性与自然光学活性均可用介质对左右圆偏振光的吸收之差来表示 .但自然光学活性和磁光学活性的物理机制是截然不同的 ,前者源于镜象不能互相重叠介质的非定域光学响应 ( nonlocaloptical response) ,而后者则是由于介质的时间反演对称性 ( time- reversal symmetry)被磁场打破所致 .理论分析表明 ,当介质的两种光学活性同时存在时 ,将会出现一个新的附加光学效应 ,这种磁光学活性与自然光学活性之间的交叉效应称为磁手性效应 ( magneto- chiral effect)或磁手二色性 ( magneto-chiral dichroism) [1,2 ] .磁手性效应通常很弱 ,直到 1…     

A Pyrene-Modified Serinol Nucleic Acid Nanostructure Converts the Chirality of Threoninol Nucleic Acids into Circularly Polarized Luminescence Signals

Herein is reported a circularly polarized luminescent (CPL) probe that can respond to the chirality of nucleic acids. An achiral nanostructure was prepared by the hybridization of symmetric serinol nucleic acid (SNA) containing pyrene-modified residues. When chiral oligomers that were complementary to the SNA were added, they induced helicity into the SNA nanowire. Efficient circular dichroism (CD) signal amplification was observed when pyrene was attached to uracil bases through a rigid alkynyl linker. Both CPL and CD signals were observed; they depended on the chirality of the added acyclic threoninol nucleic acid (aTNA) oligomer. This system can be used to convert the chirality of chiral biomolecules into chiroptical signals.     

含三氟甲基偶氮生色团环氧树脂类聚合物合成和光致表面自结构研究

利用后重氮偶合反应,将4-(三氟甲基)苯胺的重氮盐与两种具有高苯胺残基密度的环氧树脂类前体聚合物在极性有机溶剂中反应,制备了两种具有高生色团密度的环氧树脂类偶氮聚合物PEP-AZ-CF3和PEP-35AZ-CF3.利用1H-NMR、FTIR、UV-Vis和DSC等分析方法对2种偶氮聚合物结构、热性能及吸收光谱性能进行了分析及表征.研究了在不同波长的激光(488、532及589 nm)照射下,2种偶氮聚合物薄膜光致表面自结构的形成.研究结果表明,入射激光的波长对偶氮聚合物表面自结构现象的形成有明显影响.仅在波长488 nm的偏振激光(线偏振光或圆偏振光)照射下,2种偶氮聚合物薄膜表面能观察到自结构现象.圆偏光比线偏光更有利于诱导表面起伏结构的形成,但形成的表面结构不具备长程取向有序性.聚合物生色团中偶氮键邻位的取代甲基对表面自结构的形成起到阻碍作用.     

Circularly Polarized Luminescence from Simple Organic Molecules

This article aims to show the identity of “circularly polarized luminescent active simple organic molecules” as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non‐aggregated) organic molecules able to emit left‐ or right‐circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.     

FTIR measurements of optical rotatory dispersion and circular dichroism

FTIR methods for measuring optical rotatory dispersion (ORD) and circular dichroism (CD) were developed. The measurements of both phenomena are accomplished by means of various techniques. The study of ORD makes use of linearly polarized IR radiation while that of CD requires a circular polarizer (retarder) able to convert linearly polarized IR radiation into circularly polarized one. Examples of induced cholesteric solutions are shown.     

Induction of Strong and Tunable Circularly Polarized Luminescence of Nonchiral,Nonmetal, Low‐Molecular‐Weight Fluorophores Using Chiral Nanotemplates

A new strategy is described for generating strong circularly polarized luminescence with highly tunable emission bands through chiral induction in nonchiral, totally organic, low‐molecular‐weight fluorescent dyes by chiral nanotemplate systems. Our approach allows the first systematic investigation to clarify the correlation between the circular dichroism and circularly polarized luminescence intensities. As a result, a dilute solution system with the highest circularly polarized luminescence intensity achieved to date and a dissymmetry factor of over 0.1 was identified.