Circularly Polarized Luminescence and Circular Dichroism of Bichromophoric Difluoroboron-β-diketonates: Inversion and Enhanced Chirality Based on Spatial Arrangements and Self-Assembly

We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher g_abs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the g_lum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the g_lum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores.     

Molecular Design,Circularly Polarized Luminescence,and Helical Self‐Assembly of Chiral Aggregation‐Induced Emission Molecules

Aggregation‐induced emission luminogens (AIEgens) are a new class of luminophors, which are non‐emissive in solution, but emit intensively upon aggregation. By properly designing the chemical structures of the AIEgens, their aggregation process can be tuned towards a desired direction to give diverse novel luminescent architectures of micelles, rods, and helical fibers. AIEgens represent a kind of promising building block for the fabrication of luminescent micro/nanostructures with controllable morphologies. In this review, we describe our recent work in this research area, focusing on the molecular design, circularly polarized luminescence properties, and helical self‐assembly behavior of AIEgens.     

A Smart Sensing Method for Object Identification Using Circularly Polarized Luminescence from Coordination‐Driven Self‐Assembly

The potential use of circularly polarized luminescence for object identification in a sensor application is demonstrated. New luminescence probes using pyrene derivatives as sensor luminophores were developed. (R,R)‐Im₂Py and (S,S)‐Im₂Py contain two chiral imidazole moieties at 1,6‐positions through ethynyl spacers (angle between spacers ca. 180°). The probe molecules spontaneously self‐assemble into chiral stacks (P or M helicity) upon coordination to metal ions with tetrahedral coordination (Zn²⁺). The chiral probes display neither circular dichroism (CD) nor circularly polarized luminescence (CPL) without metal ions. However, (R,R)‐Im₂Py and (S,S)‐Im₂Py exhibit intense chiroptical activity (CD and CPL) upon self‐assembly with Zn²⁺ ions. (R,R)‐Im₂Py and (S,S)‐Im₂Py with chemical stimuli‐responsibility allow sensing using the CPL signal as detection output, enabling us to discriminate between a signal from the target analyte and that from non‐target species.     

Crystal structure and spectroscopic properties of ammonium hydrogensquarate squaric acid monohydrate

The structure of ammonium hydrogensquarate squaric acid monohydrate has been determined by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group C2/c and exhibits a 3D network with molecules linked by intermolecular interactions with participation of the H₂Sq, HSq^?, NH₄ ⁺, and H₂O species. The HSq^? anion and the neutral H₂Sq form a strong head-to-tail dimer through O–H···O hydrogen bonding with lengths of 2.587 and 2.494 Å (protected space between numeral and unit). The layers are connected by ammonium cations and water molecules in a plane through the O···N (2.950, 2.978, 3.036 Å) and O···O (2.953, 2.781 Å) bonds. Another such layer is connected to the NH₄ ⁺ cation in the adjacent plane through bifurcated N–H···O hydrogen-bonding to form a double layer (NH···O bond lengths are 3.036, 2.978, 2.857, 2.909, 2.958, and 2.742 Å, respectively). The IR-band assignment of the compound was achieved using the polarized IR-spectroscopy of oriented colloids in a nematic host. Theoretical ab initio calculations were performed and achieved with a view to explain the IR-bands of the H₂Sq.HSq^? motif.     

New Types of Planar Chiral [2.2]Paracyclophanes and Construction of One‐Handed Double Helices

New types of planar chiral (R_p)‐ and (S_p)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were synthesized from racemic 4,12‐dihydroxy[2.2]paracyclophane as the starting compound. Regioselective dibromination and transformation afforded a series of planar chiral (R_p)‐ and (S_p)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes, which can be used as chiral building blocks. In this study, left‐ and right‐handed double helical structures were constructed via chemoselective Sonogashira–Hagihara coupling. The double helical compounds were excellent circularly polarized luminescence (CPL) emitters with large molar extinction coefficients, good photoluminescence quantum efficiencies, and large CPL dissymmetry factors.     

Wollaston式多光束分束棱镜的设计研究

基于方解石晶体的光学特性和传统Wollaston棱镜的结构特点,设计了一种新型Wollaston式多光束分束棱镜。棱镜的两块晶体的光轴不再是垂直的,而是呈现一定的角度。通过结合玻璃棱镜,可以实现三束或四束光束平行光束的出射。以晶体光轴夹角为45°角为例,对该棱镜进行了讨论研究。研究得出:当一束自然单色光入射时,当入射光束的光斑大小大于两平行光束之间的距离时,可以实现两束相互垂直的偏振光和一束自然光出射,当光斑大小小于棱镜中两平行光束之间的距离时,能够产生四束分开程度可调并且平行出射的偏振光。该棱镜能为不同的应用环境提供可调节的偏振出射光束,从而节约成本。     

矿物流场冲击与极性吸附作用产物的红外光谱研究

 在马赫数M≥3冲击作用下和偶极矩大于或等于2.0极性分子的表面吸附作用条件下,对比了7种重要矿物微粒的红外吸收光谱特征及其变化,分析了7种矿物微粒的力学-结构效应以及表面基团的转化过程。     

Fluorescence Properties of Intercalating Neutral Chromophores in Complexes with Polynucleotides of Various Base Compositions and Secondary Structures

Changes in the relative quantum yield and polarization degree of steady-state fluorescence of daunomycin (DM) on its binding to six synthetic single- and double-stranded polynucleotides of various nucleotide compositions were measured over a wide range of molar polymer-to-dye ratios, in solutions of low ionic strength. Guanine base was found to be an effective quencher of DM fluorescence [in the DM–poly(G) complex the intensity of residual emission was ~0.5% of the free dye intensity]. The quenching of DM fluorescence by another purine base, i.e., adenine, was also revealed. But, unlike guanine, adenine exhibits quenching activity when it is in close contact with the DM chromophore, as realized in the complex with single-stranded poly(A). In intercalative complexes with double-stranded nucleic acids, where such contact is lacking, the quenching ability of adenine does not manifest itself, which has been demonstrated with the DM–poly(A) · poly(U) complex. It was found that the interaction with pyrimidine bases does not substantially change the DM quantum yield. The quenching feature of DM fluorescence is identical to that observed earlier by us for a glycoside phenazine dye containing, like DM, a neutral chromophore.     

椭圆偏振光直接实验证的数据处理方法

从理论上分析了大学物理吉有关在椭圆偏振光实验里得不到椭圆曲线的原因,提出了得到椭圆曲线的数据处理方法。