Advanced materials based on polymer cocrystalline forms

Polymeric “cocrystalline forms,” that is, structures were a polymeric host and a low‐molecular‐mass guest are cocrystallized, were early recognized, and in many cases also well characterized by X‐ray diffraction studies. However, only in the last two decades cocrystalline forms have received attention in material science, due to the ability (of few of them) to maintain an ordered polymer host structure even after guest removal, thus leading to the formation of “nanoporous‐crystalline forms,” for which many applications in the fields of molecular separation and sensors have been proposed. Moreover, in the last decade, an accurate control of the orientation of the polymer cocrystalline phases has been achieved, thus leading to a control of the orientation of the guest molecules, not only in the crystalline phase but also in macroscopic films. In addition, on the basis of this orientation control, in the last few years, cocrystalline films where active molecules are present as guests of polymer cocrystalline phases have been proposed for optical, magnetic and electric applications. In the last few years, it has been also discovered that polymer cocrystallization, when induced by nonracemic guest molecules, can produce stable chiral optical films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

The effect of chiral doping in achiral smectic liquid crystals on the de Vries characteristics: smectic layer thickness,electro-optics and birefringence

An addition of chiral dopant to two achiral smectic liquid crystals from a homologous series, by varying weight percentages with known low values of layer shrinkage, leads to chiral smectic-C* phase with a finite value of the spontaneous polarisation. The electro-optical response arising from changes in the induced apparent tilt angle brought about by a weak electric field in the SmA* phase gives rise to power law dependency on the reduced temperature. The critical exponent γ of the power law depends on the dopant concentration but its value is found to be greater than the typical value of 1.32. This implies that the short-range correlation extends from two dimensions to three dimensions in these materials in the SmA phase. The layer thickness of smectic layers in the guest–host system remains unaltered up to the 15 wt % addition of the chiral dopant to two achiral smectics. The system thus retains the low layer shrinkage of the achiral smectic as evidenced by measurements of the layer thickness from X-ray scattering and thickness measurements from optical interferometry. Results on the optical birefringence and the apparent tilt angle lead us to the conclusion of having successfully obtained chiral smectic materials for devices with de Vries characteristics by chiral doping.     

A microscopic model considering the effect of molecular biaxiality on ferroelectric ordering of liquid crystalline smectic C* phases

On the basis of a mean-field approach, a microscopic model is presented to explain some ferroelectric properties of induced smectic C* phases of chiral dipolar guest molecules in an achiral smectic C host phase. The molecular biaxiality of the chiral dopants has been taken into account, resulting in a polar and quadrupolar ordering of the molecular short axes in the rotational distribution function of the guest molecules. This model explains the dependence of the magnitude and sign of the spontaneous polarization on the molecular structure of a series of cyclo-hexanone derivatives used as chiral dopants, as well as the effect of a local field at higher dopant concentrations.     

Supramolecular chirogenesis in zinc porphyrins: interaction with bidentate ligands,formation of tweezer structures,and the origin of enhanced optical activity

The complexation behavior, binding properties, and spectral parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral bidentate guests (diamines and amino alcohols) have been studied by means of UV-vis, CD, fluorescence, (1)H NMR, and ESI MS techniques. It was found that the guest structure plays a decisive role in the chirogenesis pathway. The majority of bidentate ligands (except those geometrically unsuitable) exhibit two major equilibria steps: the first guest ligation leading to formation of the 1:1 host-guest tweezer structure (K(1)) and the second guest molecule ligation (K(2)) forming the anti bis-ligated species (1:2). The second ligation is much weaker (K(1) > K(2)) due to the optimal geometry and stability of the 1:1 tweezer complex. The enhanced conformational stability of the tweezer complex ensures an efficient chirality transfer from the chiral guest to the achiral host, consequently inducing a remarkably high optical activity in the bis-porphyrin.     

Chiral Recognition and Separation by Chirality‐Enriched Metal–Organic Frameworks

Endowed with chiral channels and pores, chiral metal–organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality‐enriched MOFs with accessible pores. The ability of the materials to form host–guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed‐matrix membranes (MMMs) composed of chirality‐enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation.     

Excited-state optical activity of a cyclodextrin inclusion compound

The optical activity of the inclusion compound formed when fluorescein is incorporated in β-cyclodextrin has been studied by means of circularly polarized luminescence spectroscopy. The chiral host molecule is capable of inducing chirality in the achiral guest molecule upon formation of the 1:1 adduct.     

Quantified chirality, molecular similarity, and helical twisting power in lyotropic chiral nematic guest/host systems

Lyotropic liquid crystals can exhibit phase chirality. The mechanism behind the transfer of chirality between a chiral dopant and a liquid crystalline host phase is still under discussion. Our own recent results and proposals are the following. Lyotropic phase chirality can exist even at very low concentrations of chiral dopants, with less than 1 chiral dopant per 50 micelles. There is evidence for an intramicellar double twist which could be due to the induction of chiral conformations in the achiral surfactant chains. The chirality of arbitrary molecules can be quantified by means of the 'Hausdorff distance'. Increasing chirality of a dopant does not necessarily imply increasing helical twisting power, and molecular similarity between chiral guest and achiral host is essential for effective chirality transfer.     

Enhanced ordering in polymer stabilised ferroelectric liquid crystal guest–host composites: evidence by polarised fluorescence spectroscopy

Guest–host polymer stabilised ferroelectric liquid crystal (PSFLC) composite films have been prepared by polymerisation-induced phase separation process. A small quantity (0.1, 0.25 and 0.5 wt %) of anthraquinone dye in PSFLC host matrix was homogeneously dispersed to create molecular ordering in fibrils network of guest–host composite film. Ordered twisted fibril morphology was clearly observed through optical polarising microscope and thus we determined the order parameter from the dichroism measurements with the help of polarised fluorescence spectroscopy, which impacts the significant contribution of dye molecules into the smectic layers of the host polymer stabilised ferroelectric matrix.     

Ferroelectricity of induced S*C phases with novel chiral dopants

Induced S*_C phases can be obtained by dissolving chiral dopants in achiral S_C host phases. If the chiral guest molecules bear a transverse dipole, ferroelectricity will occur. The novel dopants under discussion are characterized by chiral centres and the transverse dipole situated not in the alkyl end groups of the mesogenic molecules, but directly in their rigid cores. As a rigid core, analogues of decalin were used. In those dopants, rotation around the molecular long axis is sterically restricted. According to the microscopic model of Zeks, this leads to enhanced values of the spontaneous polarization P_s. The magnitude as well as the sign of the spontaneous polarization P_s of the S*_C phases induced by the novel dopants in different host phases has been investigated. It has been found for the first time that for a given dopant, the polarization as well as the sign of P_s depends on the structure of the host phase. The results are discussed in terms of two microscopic models. They can be understood taking into account the situation that the potential of the restricted long axial rotation is determined by the hard core interactions of the molecules involved or that an orientation of the host dipoles by a guest/host interaction takes place.     

Ferroelectricity of induced S*C phases with novel chiral dopants

Abstract

Induced S*_C phases can be obtained by dissolving chiral dopants in achiral S_C host phases. If the chiral guest molecules bear a transverse dipole, ferroelectricity will occur. The novel dopants under discussion are characterized by chiral centres and the transverse dipole situated not in the alkyl end groups of the mesogenic molecules, but directly in their rigid cores. As a rigid core, analogues of decalin were used. In those dopants, rotation around the molecular long axis is sterically restricted. According to the microscopic model of Zeks, this leads to enhanced values of the spontaneous polarization P _s. The magnitude as well as the sign of the spontaneous polarization P _s of the S*_C phases induced by the novel dopants in different host phases has been investigated. It has been found for the first time that for a given dopant, the polarization as well as the sign of P _s depends on the structure of the host phase. The results are discussed in terms of two microscopic models. They can be understood taking into account the situation that the potential of the restricted long axial rotation is determined by the hard core interactions of the molecules involved or that an orientation of the host dipoles by a guest/host interaction takes place.     

含手性末端基偶氮聚合物膜的全息光栅研究

偶氮苯侧链型高分子由于其含有偶氮苯基团 ,在光作用下会发生可逆的顺反异构过程 ,具有光致取向特性 ,在光学处理、衍射光学、投影显示、光开关等许多方面具有潜在的应用性[1] .近 1 0多年来国内外学者对此类化合物进行了广泛的研究 ,已有文献报道可利用Ａｒ+激光束在偶氮苯聚合物薄膜上直接“写入”表面凸起光栅 ,并且通过原子力显微镜观测到光栅起伏 .这种光栅很稳定 ,并可以利用光学方法“擦去” .偶氮苯聚合物上述独有的性质引起了许多学者的兴趣[2 ,3] .另一方面 ,由于旋光性聚合物在光学物理性质上的优势 ,我们已将手性基团引入偶氮苯…     

Stereospecific change in conformation upon complexation of an exoditopic tetraamide host with a bis(ammonium) guest: chiral recognition and strong CD signaling

Upon complexation of a rectangular-shaped achiral macrocyclic host with chiral guests, twisting deformation occurs to induce exciton-type bisignated CD, whereas a chiral rectangular host undergoes a similar structural change only with the matching enantiomer of a chiral guest.     

Steric communication of chiral information observed in dendronized polyacetylenes

Structural and retrostructural analysis of helical dendronized polyacetylenes (i.e., self-organizable polyacetylenes containing first generation dendrons or minidendrons as side groups) synthesized by the polymerization of minidendritic acetylenes with [Rh(nbd)Cl]2 (nbd = 2,5-norbornadiene) reveals an approximately 10% change in the average column stratum thickness (l) of the cylindrical macromolecules with a chiral periphery, through which a strong preference for a single-handed screw-sense is communicated. The cylindrical macromolecules reversibly interconvert between a three-dimensional (3D) centered rectangular lattice (Phi r-c,k) exhibiting long-range intracolumnar helical order at lower temperatures and a two-dimensional (2D) hexagonal columnar lattice (Phi h) with short-range helical order at higher temperatures. A polymer containing chiral, nonracemic peripheral alkyl tails is found to have a larger l as compared to the achiral polymers. In methyl cyclohexane solution, the same polymer exhibits an intense signal in circular dichroism (CD) spectra, whose intensity decreases upon heating. The observed change in l indicates that the chiral tails alter the polymer conformation from that of the corresponding polymer with achiral side chains. This change in conformation results in a relatively large free energy difference (DeltaGh) favoring one helix-sense over the other (per monomer residue). The capacity to distort the polymer conformation and corresponding free energy is related to the population of branches in the chiral tails and their distance from the polymer backbone by comparison to recently reported first and second generation dendronized polyphenylacetylenes.     

Heterocomplexation of a chiral dipeptide and quantitative enantiomeric enrichment of nonracemic 1,1'-bi-2-naphthol

Heterocomplexation of a chiral host to a racemic guest has been discovered. A cyclic dipeptide generated from (S)-proline alkyl ester undergoes an achiroselective complexation to both the enantiomers of racemic BINOL in benzene to yield a crystalline heterocomplex bearing the solvent molecules. However, complexation crystallization does not occur between the diptide and either enantiomer of BINOL under similar conditions. The difference in complexation behavior has been successfully applied in the enantiomeric enrichment of nonracemic BINOLs, and almost quantitative separation of the excess enantiomer from racemic BINOL was achieved.     

The use of thermal techniques in the determination of the phase diagram of lanthanide salt based polymer electrolytes

Differential thermal analysis, optical microscopy and ionic conductivity studies have been carried out on polymer electrolyte films prepared by deposition of solutions of neodymium trifluoromethanesulphonate and poly(ethylene oxide). A wide range of electrolyte concentrations were examined and a partial pseudo-equilibrium phase diagram of the system was determined. From the results obtained it is evident that the presence of relatively high concentrations of ionic guest species in the polymer host results in an inhibition of the growth of crystalline material (polymer spherulites or a polymer—salt coordination complex).     

Phase behavior and anisotropic optical properties of photoluminescent polarizers

The phase behavior and anisotropic optical properties of tensile deformed blends of a photoluminescent polymer guest in an ultra‐high molecular weight polyethylene matrix were studied on the level of single molecules by means of scanning confocal optical microscopy. It is shown that upon tensile deformation of the blends, the system transforms from a phase‐separated system into a quasi‐molecular solid solution. The influence of this phase transition on the anisotropic optical properties of oriented blend films was also investigated with polarized steady‐state photoluminescence spectroscopy. We show that well‐dissolved guest molecules tend to reach higher degrees of orientation at lower draw ratios of the blend films compared to guests that phase‐separate from the matrix polymer. Dichroic ratios in emission in the range of 50 were observed in optimized blend films based on photoluminescent oligomers and linear low density polyethylene.     

Host–guest complexation‐triggered chiroptical change of poly(phenylacetylene)s bearing binaphthocrown ether moieties on the main chain

Diacetylene monomers with respective lengths of the oxyethylene chains were cyclopolymerized with a rhodium catalyst to produce novel poly(phenylacetylene)s bearing a different cavity size of the chiral crown ether in the repeating units ( 2a – c ). In the circular dichroism spectra of the resulting polymers, characteristic Cotton effects were observed in the range from 350 to 500 nm corresponding to the absorption of the conjugated polymer backbone, indicating that the polymers possessed a helical structure with an excess single screw sense induced by the covalently bonded binaphthyl units. The host–guest complexation of 2a – c with achiral guests produced a chiroptical change based on the fluctuation in the main chain conformation. The behavior of the complexation‐induced chiroptical change was essentially dictated by the cavity size of the binaphthocrown ether units. Additionally, a chirality‐responsive helicity change was observed in the case of the complexation of 2a – c with chiral guests, which also depended on the crown ether size. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1197–1206, 2010     

Induction of supramolecular chirality in di-zinc(II) bisporphyrin via tweezer formation: synthesis, structure and rationalization of chirality

Two new supramolecular complexes consisting of an achiral bisporphyrin host and a chiral diamine guest are reported. One shows a remarkably high amplitude bisignate CD signal while the other one shows a very low value. X-ray structure and other spectroscopic investigations of the tweezer complexes clearly rationalize the origin of the optical activity that has so far remained an unresolved issue.     

Homo‐double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines

An optically active, m‐terphenyl‐based π‐conjugated polymer bearing carboxy groups was synthesized by the copolymerization of the diethynyl monomer bearing a carboxy group with (S,S)‐2,5‐bis(2‐methylbutoxy)‐1,4‐dibromobenzene using Sonogashira reaction. The copolymer showed a weak circular dichroism (CD) in the main‐chain chromophore region due to a homo‐double helix formation with an excess helical handedness biased by the chiral alkoxy substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double helix was also induced in the polymer in the presence of nonracemic amines. The effect of the achiral and chiral amines on the homo‐double helix formation was investigated by comparing the CD spectra of the polymer to those of its model dimer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 990–999     

Photo‐optical properties and photo‐orientation phenomena in an immiscible blend of cholesteric copolymer with azobenzene‐containing polymer

Novel side chain liquid crystalline polymer blends containing immiscible non‐chiral and cholesteric polymers were prepared. A non‐chiral polymer was used containing azobenzene side groups capable of E–Z photoisomerization. Phase behaviour and miscibility properties of the blends were studied. Thin films of the blends were prepared by spin‐coating; it was shown that just after preparation these films are optically isotropic and homogeneous. Photo‐ and chiro‐optical properties of the films as well as photo‐orientation phenomena induced by the action of polarized light were investigated. It was found that the photo‐optical behavior of these films is rather complicated and considerably different from the properties of both individual components. This difference is associated with the strong influence of blend morphology on the photo‐optical properties.