Anisotropic Poisson Effect and Deformation‐Induced Fluorescence Change of Elastic 9,10‐Dibromoanthracene Single Crystals

Elastic organic crystals have attracted considerable attention as next‐generation flexible smart materials. However, the detailed information on both molecular packing change and macroscopic mechanical crystal deformations upon applied stress is still insufficient. Herein, we report that fluorescent single crystals of 9,10‐dibromoanthracene are elastically bendable and stretchable, which allows a detailed investigation of the deformation behavior. We clearly observed a Poisson effect for the crystal, where the short axes (b and c‐axes) of the crystal are contracted upon elongation along the long axis (a‐axis). Moreover, we found that the Poisson's ratios along the b‐axis and c‐axis are largely different. Theoretical molecular simulation suggests that the tilting motion of the anthracene may be responsible for the large deformation along the c‐axis. Spatially resolved photoluminescence (PL) measurement of the bent elastic crystals reveals that the PL spectra at the outer (elongated), central (neutral), and inner (contracted) sides are different from each other.     

Porous and Shape‐Anisotropic Single Crystals of the Semiconductor Perovskite CH3NH3PbI3 from a Single‐Source Precursor

Significant progress in solar‐cell research is currently made by the development of metal–organic perovskites (MOPs) owing to their superior properties, such as high absorption coefficients and effective transport of photogenerated charges. As for other semiconductors, it is expected that the properties of MOPs may be significantly improved by a defined nanostructure. However, their chemical sensitivity (e.g., towards hydrolysis) prohibits the application of methods already known for the synthesis of other nanomaterials. A new and general method for the synthesis of various (CH₃NH₃)PbI₃ nanostructures from a novel single‐source precursor is presented. Nanoporous MOP single crystals are obtained by a crystal‐to‐crystal transformation that is accompanied by spinodal demixing of the triethylene glycol containing precursor structure. Selective binding of a capping agent can be used to tune the particle shape of the MOP nanocrystals.     

二维Bi2Se3晶体对罗丹明6G分子的荧光猝灭效应研究

首次研究了拓扑绝缘体Bi₂Se₃二维晶体对其表面吸附的罗丹明6G分子的荧光猝灭效应, 证明薄层Bi₂Se₃可以有效猝灭罗丹明6G分子的荧光, 且随Bi₂Se₃二维晶体的厚度从单层增加到8层, 荧光猝灭效应增强, 并初步探讨了其荧光猝灭机理.     

Elastic Organic Crystals of a Fluorescent π‐Conjugated Molecule

An elastic organic crystal of a π‐conjugated molecule has been fabricated. A large fluorescent single crystal of 1,4‐bis[2‐(4‐methylthienyl)]‐2,3,5,6‐tetrafluorobenzene (over 1 cm long) exhibited a fibril lamella morphology based on slip‐stacked molecular wires, and it was found to be a remarkably elastic crystalline material. The straight crystal was capable of bending more than 180° under applied stress and then quickly reverted to its original shape upon relaxation. In addition, the fluorescence quantum yield of the crystal was about twice that of the compound in THF solution. Mechanical bending–relaxation resulted in reversible change of the morphology and fluorescence. This research offers a more general approach to flexible crystals as a promising new family of organic semiconducting materials.     

Surface Fixing Effect of Vacuum Evaporated Particles on Polyethylene Single Crystals

Summary: The recrystallization behavior of high density polyethylene (HDPE) single crystals with vacuum evaporated metal chromium or carbon on their surface has been investigated by transmission electron microscopy (TEM) and electron diffraction (ED) techniques. The results indicate that the particle‐coated HDPE single crystals can retain their single crystal structure after complete melting and subsequent recrystallization, with the heat‐treated temperature as high as 200 °C. This phenomenon is attributed to a surface fixing effect of vacuum evaporated Cr or carbon on the single crystals.

A bright‐field electron micrograph and the corresponding electron diffraction pattern of recrystallized Cr‐coated HDPE single crystals.     

Simultaneous Quantitation of Three Aromatic Compounds by Fluorescence Spectroscopy and Elastic Component Regression

The determination of aromatic compounds is of importance in many fields. Even if these compounds may be determined by molecular fluorescence and second-order calibration, the methods are relatively complex and require higher mathematics. Here is explored whether the reduction of the dimensions, i.e., transforming two-dimensional data to one-dimensional data followed by a special variable selection and calibration process, is feasible for this purpose. The present work investigated the feasibility of combining competitive adaptive reweighted sampling and elastic component regression for the direct evaluation of the spectra to quantify three components simultaneously. Model population analysis has also been performed. The results confirmed the feasibility of the procedure, which may serve as an alternative method to simultaneously determine aromatics.     

Three Rings Schiff Base Ester Liquid Crystals: Experimental and Computational Approaches of Mesogenic Core Orientation Effect,Heterocycle Impact

Three rings 2-hydroxypyridine liquid crystalline compounds have been prepared and fully characterized. The mesomorphic behavior of the prepared compounds has been investigated in terms of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Moreover, a comparative study between the prepared compounds and previously reported analogs has been discussed in terms of the orientation and position of the mesogenic core, in addition to the direction of the terminal alkyl chains. Furthermore, a detailed computational approach has been studied to illustrate the effect of geometrical and dimensional parameters on the type of the enhanced texture and the mesomorphic range and stability. The results of the DFT study revealed that the orientation of the mesogen could affect the mesomorphic behavior and this has been attributed in terms of the degree of the polarizability of the linking groups. This result has been confirmed by calculation of the net dipole moment and the molecular electrostatic potential that show how the mesogen orientation and position could impact the molecular charge separation. Finally, the effect of the pyridyl group has been also investigated in terms of the calculated aromaticity index and the π-π stacking.     

Thermo-Induced Single-Crystal-to-Single-Crystal Transformations and Photo-Induced [2+2] Cycloaddition Reactions in Polymorphs of Chalcone-Based Molecular Crystals: Multi-Stimuli Responsive Actuators

The polymorphs of 2ClChMe-4 in Form I (ribbon-like crystal) and Form II (block-like crystal) were prepared, and they exhibited curling/flipping and expansion upon heating on account of single-crystal-to-single-crystal transformations. The irreversible phase transformations occurred separately at 53.2 °C and 57.8 °C for the crystals in Form I and Form II, during which the molecular conformation of 2ClChMe-4 changed and the molecules slipped along the (100) plane. Movement at the molecular level resulted in changes of cell parameters, which in turn led to macroscopic motions of the crystals upon heating. Additionally, the ribbon-like crystals of 2ClChMe-4 showed photo-induced bending driven by [2+2] cycloaddition. Accordingly, an actuator showing reversible bending behavior was fabricated triggered by light and heat successively. Like biomimetic self-actuators, such multi-stimuli mechanical responsive molecular crystals might have potential applications in soft robots, artificial muscles and microfluidic systems.     

Polymorph‐Dependent Green,Yellow, and Red Emissions of Organic Crystals for Laser Applications

Color tuning of organic solid‐state luminescent materials remains difficult and time‐consuming through conventional chemical synthesis. Herein, we reported highly efficient polymorph‐dependent green (P1), yellow (P2), and red (P3) emissions of organic crystals made by the same molecular building blocks of 4‐(2‐{4‐[2‐(4‐diphenylamino‐phenyl)‐vinyl]‐phenyl}‐vinyl)‐benzonitrile (DOPVB). Single‐crystal X‐ray diffraction (XRD) and spectroscopic data reveal that all three polymorphs follow the herringbone packing motif in H‐type aggregations. On the one hand, from P1, P2 to P3, the reduced pitch translation along π stacks increases the intermolecular interactions between adjacent molecules, therefore leading to gradually red‐shifted emissions from 540, 570 to 614 nm. On the other hand, the edge‐to‐face arrangement and large roll translations avoid strong π–π overlap, making P1, P2 and P3 highly emissive with record‐high solid‐state fluorescence quantum yields of 0.60, 0.98, and 0.68, respectively. Furthermore, the optically allowed 0–1 transitions of herringbone H‐aggregates of P1, P2 and P3 naturally provide a four‐level scheme, enabling green and yellow amplified spontaneous emissions (ASE) with very low thresholds.     

Effect of some organic solvents and acids on the laser-induced atomic fluorescence of tin in air-hydrogen flames

The effects of some organic solvents and acids on the atomic fluorescence of tin in air-hydrogen flames have been examined. Ketones and alcohols greatly reduced the florescence sensitivity in fuel rich air-hydrogen flame whereas organic acids generally enhanced the fluorescence signal. The depressive effect of organic solvents was found to be highly dependent on the fuel to oxidant ratio in the flame. An attempt has been made to explain these effects, on the basis of possible reactions occurring in the flame.On leave from Institute of Chemistry, University of the Punjab, Lahore 54590, PakistanOn leave from Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain     

Matrix Effect of Alkali and Alkaline Earth Metal Halides on Fluorescence Quantum Yield of Indium in Laser‐Induced Fluorescence Flame Spectrometry

As interfered with by alkali and alkaline earth metal halides added as the matrix in an acetylene/air flame, the fluorescence quantum yield of In as the analyte in a laser‐induced fluorescence (LIF) flame spectrometry has been thoroughly characterized. The fluorescence quantum yield is determined by a ratio of F to A, where F is the measured fluorescence of In and A is the difference between the absorption signals recorded for the analyte and the blank solutions. The normalized fluorescence signal is treated to prevent deviations due to variations of the atomization efficiency under the conditions with and without the matrix added. The fluorescence quantum yield is measured to be almost independent of the matrix concentration up to 500 ppm (μg/mL) studied, under conditions of either optical unsaturation or saturation. By considering a quenching effect induced by electron‐atom collisions, the calculated fluorescence quantum yields are consistent with our observations.     

External Heavy‐Atom Effect on the Prompt and Delayed Fluorescence of [70]Fullerenes

The influence of the external heavy‐atom effect (HAE) on the fluorescence properties of C₇₀ and a C₇₀ methano monoadduct is determined. For this purpose the photophysics of these [70]fullerenes is studied in polystyrene (PS) and in a related heavy‐atom polymer, poly(4‐bromostyrene) (PBS). In the absence of HAE (PS matrix) both fullerenes display a strong thermally activated delayed fluorescence (DF) that is more pronounced in the case of C₇₀. In the presence of HAE (PBS matrix) both prompt (PF) and DF intensities decrease significantly, the same happening to the delayed fluorescence lifetimes. The relative fluorescence intensities (DF intensity/PF intensity) for each fullerene are on the other hand surprisingly similar to the respective ones in PS for the full experimental temperature range. The HAE is responsible for a significant increase of the S₁→T₁ and S₁←T₁ intersystem crossing (ISC) rates, and of the T₁→S₀ radiative rate. In particular, the HAE on a S₁←T₁ ISC rate is reported here for the first time. The overall substantial insensitivity of relative fluorescence intensities to HAE is explained by a compensation effect: As the S₁→T₁ and S₁←T₁ ISC rates on the one hand, and the T₁→S₀ radiative rate on the other hand work in opposition with respect to DF, a near cancellation of effects occurs.     

CdTe量子点与蛋白质相互作用的荧光猝灭效应

本文在水热法合成水溶性CdTe及核壳结构CdTe/CdS量子点的基础上,分别研究了细胞色素c对CdTe量子点及CdTe/CdS核壳量子点荧光的猝灭效应和CdTe量子点对牛血清白蛋白荧光的猝灭效应,并阐述了猝灭机理。结果显示,细胞色素c对CdTe量子点的荧光猝灭效应具有一定的粒径依赖性,粒径越小,猝灭效应越强;细胞色素c对CdTe/CdS核壳量子点的猝灭效应比对CdTe量子点的更强,揭示了受激电子的表面传递机理。CdTe量子点通过松散牛血清白蛋白的螺旋结构而猝灭其荧光。     

Bending,Curling, Rolling,and Salient Behavior of Molecular Crystals Driven by [2+2] Cycloaddition of a Styrylbenzoxazole Derivative

We report interesting photomechanical behaviors of the dynamic molecular crystals of (E )‐2‐(2,4‐dichlorostyryl)benzo[d]oxazole ( BOACl24 ). The photosalient effect of the rod‐like crystal based on a metal‐free olefin driven by photodimerization is observed. Moreover, the needle‐like crystals of BOACl24 exhibit a reversible bending away from a UV light source. The nanofibers curl easily under UV irradiation in an organogel, in which the photo‐induced rolling of a small slice occurs. This suggests that the rapid release of the accumulated strain during photodimerization may lead to a photosalient effect, and the bending or curling happens when the strain is released slowly. Notably, [2+2] cycloaddition takes place between two different conformational isomers of BOACl24 on account of the rotation of the benzoxazole ring around the C−C bond in an excited state before photodimerization. Such topo‐photochemical reaction has not been reported elsewhere.     

Supramolecular Assembly and Headgroup Effect in Interfacial Organized Films (II): A Study of Some Single Chain Amphiphiles

Some single chain Schiff bases amphiphiles with different substituted headgroups have been designed and their interfacial phase behaviors and coordination with Cu(II) ions were investigated. It has been found that depending on the size of aromatic headgroups, the formed nanostrucures showed obvious differences, indicating different aggregation behaviors in the Langmuir-Blodgett films. The spreading Cu(II)-coordinated films could be transferred and subsequently characterized by spectral methods and morphological measurement. In addition, during the coordination process of ligand with Cu(II) ions in organized molecular films, some conformational change of long alkyl chains was observed. The present work showed clearly the headgroup effect of amphiphiles on regulating the aggregation behaviors in Langmuir-Blodgett films.     

苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响

New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature.     

Effect of the environment on the stability of surfactant–polypeptide self‐assembled complexes: Molecular dynamics simulations of stoichiometric complexes formed by N‐dodecyltrimethylammonium and poly(α,L‐glutamate) in chloroform,methanol, and water

A series of molecular dynamics simulations have been performed to study the supramolecular structure of self‐assembled complexes formed by N‐dodecyltrimethylammonium cations and the synthetic polypeptide poly(α,L ‐glutamate). The influence of the type of solvent has been investigated, considering explicit environments of chloroform, water, and methanol on a stoichiometric complex containing 15 residues. In chloroform, the complex stabilizes in a regular structure: the polypeptide adopts an α‐helix conformation that is regularly surrounded by surfactant molecules to form electrostatic interactions through a multiple interaction pattern. However, this structure destabilizes in methanol and water: (a) the α‐helix unfolds in the two solvents and (b) the electrostatic links between the surfactant molecules and the polyanion are disrupted in aqueous solution, although these interactions are still preserved in methanol. The role of the solvent environment in stabilizing or destabilizing the polypeptide secondary structure, the organization of the surfactant molecules, and predominantly the surfactant–polypeptide supramolecular organization is discussed in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1122–1133, 2006     

Synthesis of Mixed Tail Triphenylene Discotic Liquid Crystals： Molecular Symmetry and Oxygen-Atom Effect on the Stabilization of Columnar Mesophases

Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would result in novel mesomorphism. A series of mixed tail triphenylenes containing propoxyacetyloxy and alkoxy, abbreviated as C18H6（OCnH2n＋1）3（OCOCH2OC3H7）3, n=4-8, and hexa（propyloxyacetyloxy）triphenylene, C18H6（OCOCH2OC3H7）6 were synthesized. Thermal gravimetry analysis （TGA） of three discogens showed that they had good thermal stability till 350 ℃. The mesomorphism was investigated through differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The preliminary X-ray diffraction （XRD） results of one compound showed that it exhibited ordered hexagonal columnar （Colho） mesophase. These mixed tail triphenylene derivatives possessed much stable Colho mesophase and wider mesophase ranges than their hexaalkoxytriphenylene C18H6（OR）6 and hexaalkanoyloxytriphenylene C18H6（OCOR＇）6 analogues. The asymmetrical compounds 2,6,11-trialkoxy-3,7,10-tri（2-propyloxyacetyloxy）triphenylenes with n=5-8 displayed higher clearing points and wider temperature ranges than their symmetrical isomers 2,6,10-trialkoxy-3,7,11-tri（2-propyloxyacetyloxy）- triphenylenes, while C18H6（OCOCH2OC3H7）6 had the highest clearing point due to the β-oxygen-atom effect.