Chiral Core Research Articles

Fluorinated chiral nematic liquid crystal dimers based on (S)-1-phenylethane-1,2-diol

ABSTRACTA series of symmetric liquid crystal (LC) dimers with the same chiral core (S)-1-phenylethane-1,2-diol ((S)-PE) have been synthesised, termed TBDA-(S)-PE, 3F3B-(S)-PE, 3F2B-(S)-PE, 1F3B-(S)-PE, 1F2B-(S)-PE, respectively. Chemical structures and LC properties of the five symmetric LC dimers were characterised by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectrometer (1H NMR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and polarised optical microscopy (POM). TBDA-(S)-PE displayed enantiotropic chiral smectic A (SmA*) phase while 3F3B-(S)-PE, 3F2B-(S)-PE, 1F2B-(S)-PE all displayed enantiotropic chiral nematic (N*) phase and 1F3B-(S)-PE displayed monotropic N* phase. The results indicated that the removal of the flexible spacers between the rigid mesogenic arm and the chiral core facilitated the formation of the N* phase. When the rigid mesogenic units are connected to the chiral core directly, the structure of the terminal fluorine group and the rigidity of the mesogenic unit played certain influence on the thermal properties of the LC dimers, but did not change the type of mesomorphic phase. Compared to 3F3B-(S)-PE and 1F3B-(S)-PE, 3F2B-(S)-PE and 1F2B-(S)-PE displayed wider LC ranges, respectively, suggesting molecular regularity had greater influence on LC-isotropic (I) transition temperature.

Optimization design of chiral hexagonal honeycombs with prescribed elastic properties under large deformation

Flexible chiral honeycomb cores generally exhibit nonlinear elastic properties due to large geometric deformation. The effective elastic moduli and Poisson’s ratio typically vary with an increase in deformation. Here, the size and shape optimization of the chiral hexagonal honeycombs was performed to keep the Young’s moduli and Poisson's ratio unchanged under large deformations. The size of the honeycomb unit cell and the position coordinates of the key points were defined simultaneously as design variables. The equivalent Young's modulus and Poisson’s ratio of chiral honeycombs were calculated through geometric nonlinear analysis. The objective was to minimize the allowable tolerance between the prescribed and actual properties within the range of the target strain. A genetic algorithm was then adopted. The optimal results demonstrate that the chiral honeycombs can maintain effective elastic properties that do not vary under large deformation. These results are meaningful to morphing aircraft designs.

Self-Sorting Double-Network Hydrogels with Tunable Supramolecular Handedness and Mechanical Properties.

Self-sorting, simultaneous, and orthogonal operations during the self-assembly of complex mixtures are commonly observed for biological species but rare in artificial systems. In this study, we designed two gelators (LPF and LPFEG) containing the same chiral phenylalanine core but different achiral peripheral substituents to give hydrogels with opposite supramolecular handedness. When the two hydrogels were mixed, double-network nanofibers with opposite handedness were formed by spontaneous high-order organization and self-sorting of the two gelators. The chiroptical activity of the double-network hydrogels could be tuned by varying the molar ratio of LPF and LPFEG in the mixture, thus showing that the two gelators were highly independent of each other. Enhanced mechanical properties were observed for the interpenetrating networks when the LPF/LPFEG molar ratio was 3:7, with a more than fourfold increase in both the storage (G') and loss modulus (G'') relative to those of the individual hydrogels.

Self‐Sorting Double‐Network Hydrogels with Tunable Supramolecular Handedness and Mechanical Properties

AbstractSelf‐sorting, simultaneous, and orthogonal operations during the self‐assembly of complex mixtures are commonly observed for biological species but rare in artificial systems. In this study, we designed two gelators (LPF and LPFEG) containing the same chiral phenylalanine core but different achiral peripheral substituents to give hydrogels with opposite supramolecular handedness. When the two hydrogels were mixed, double‐network nanofibers with opposite handedness were formed by spontaneous high‐order organization and self‐sorting of the two gelators. The chiroptical activity of the double‐network hydrogels could be tuned by varying the molar ratio of LPF and LPFEG in the mixture, thus showing that the two gelators were highly independent of each other. Enhanced mechanical properties were observed for the interpenetrating networks when the LPF/LPFEG molar ratio was 3:7, with a more than fourfold increase in both the storage (G′) and loss modulus (G′′) relative to those of the individual hydrogels.

Synthesis of anti-1,3 Amino Alcohol Motifs via Pd(II)/SOX Catalysis with the Capacity for Stereodivergence.

We report the development of a Pd(II)/(±)-MeO-SOX/2,5-dimethylbenzoquinone system that enables unprecedented access to anti-1,3 amino alcohol motifs in good yields (33 substrates, avg. 66% isolated yield, >20:1 dr) and high selectivities (avg. 10:1 dr). Switching ligands to (±)-CF3-SOX with the use of a less bulky quinone oxidant, the kinetic syn-1,3 amino alcohol motif can be accessed in comparable yields and selectivities. Advantages of the stereodivergent nature of this reaction are seen in the synthesis of anti- and syn-1,3 amino alcohol vitamin D3 analogue intermediates in half the steps and higher overall yield relative to previous routes. Additionally, all eight possible stereoisomers of a chiral diamino alcohol core are generated from two amino acids. Mechanistic studies reveal that the anti-isomer is furnished through concurrent Pd(II)(SOX) catalyzed C-H amination and Pd(0)(SOX) catalyzed isomerization cycles.

Non-conventional multi-arm ester liquid crystal derived from cholic acid: synthesis, thermal and optical behaviour

ABSTRACTWith cholic acid as the core, five multi-arm ester liquid crystals were synthesised with different terminal substituents. B1–B5 were mesogenic arms which were linked to multifunctional chiral core cholic acid. The effect of electron-withdrawing and electron-donating groups on the mesogenic behaviour of the compounds was discussed. All products were structurally well characterised by elemental analysis, 1HNMR, and FT-IR. The phase behaviours were investigated by means of polarised optical microscopy and differential scanning calorimetry. B2, B4, B5 and C2, C4, C5 and D2, D4, D5 exhibited typical nematic texture and belonged to thermotropic enantiotropic nematic liquid crystals. B3, C3 and D3 also displayed typical nematic texture of thermotropic monotropic nematic liquid crystal. B1, C1 and D1 did not have mesogenic performance. Wider mesogenic range for 81.6°C of C5 whose terminal substituent is nitro on heating cycle while 121.1°C on cooling cycle. The results indicated that terminal substituents have a pretty important effect on the mesogenic phase and range of multi-arm liquid crystal compounds. The mesomorphic behaviour of compounds with polar groups terminally substituted performance much better than those without polar groups. In this ester multi-arm liquid crystal system, electron-withdrawing groups terminally substituted behave better than those electron-donating groups substituted.

Chiral Noble Metal Nanoparticles and Nanostructures

AbstractThe origins of chirality and chiroptical properties in ligand‐protected gold and silver nanoparticles (NPs) are considered herein. Current conceptual models including the chiral core model, dissymmetric field model, and chiral footprint model are described as mechanisms that contribute to the understanding of chirality in these systems. Then, recent studies on thiolate‐stabilized gold NPs, phosphine‐stabilized gold NPs, multi‐ligand‐stabilized silver NPs, and DNA‐stabilized silver NPs are discussed. Insights into the origin of chiroptical properties including reasons for large Cotton effects in circular dichroism spectra are considered using both experimental and theoretical data available. Theoretical calculations using density functional theory (DFT) and time‐dependent DFT methods are found to be extremely useful for providing insights into the origin of chirality. The origin of chirality in ligand‐protected gold and silver NPs can be considered to be a complex phenomenon, arising from a combination of the three conceptual models.

Nanoscale Chirality

Nanoparticles/nanostructures have long been attracting extensive interest thanks to their unique optical and electronic properties that are vastly different from those of their atomic and bulk forms. This material chemistry is further enriched by the recent emergence of nanoscale chirality. Traditionally, chirality refers to the handedness of a molecule or structure that is non-superimposable onto its mirror image, and can be quantitatively assessed by circular dichroism (CD) measurements. This has been observed with a range of molecules, such as peptides, proteins, and DNA, where the CD absorption typically appears in the far ultraviolet region. Recently, a variety of nanoparticles and nanostructures have also been found to exhibit unique chiroptical characteristics in the visible range due to intimate interactions with the nanoparticle surface plasmon resonance (hence denoted as plasmonic circular dichroism, PCD). Such nanoscale chirality has been observed with a chiral core shape, such as helical/spiral structures and/or the formation of chiral staples on the metal core surfaces. In addition, the strong interactions between the surface capping ligands and noble metal nanoparticles, such as gold and silver, can potentially influence the nanoparticle's surface property and give rise to chiroptical response as well. Interestingly, when the interactions between the capping ligands and the plasmonic nanoparticles are relatively weak, the symmetry of the metal core surface will not be changed appreciably upon the formation of a capping layer. In this case, the nanoparticle CD may arise from chiral organic capping ligands that are interacting with the plasmonic nanoparticles, and become intensified with increasing concentration of the chiral molecules on the nanoparticle surface. This is generally ascribed to strong dipole (and higher-order) interactions between the ligand and nanoparticle core electrons. Upon interactions with the chiral ligands, the symmetry of the electronic property of the nanoparticle core surface is distorted, leading to different extinction coefficients between the left- and right-handed circularly polarized light. In addition to individual nanoparticles, nanoparticle assembly with chiral crosslinkers can also exhibit well-defined PCD response (e.g., DNA and peptides). More interestingly, achiral nanoparticles can assemble into chiral nanostructures and produce apparent chiroptical response, even without the use of chiral crosslinkers. As the resulting PCD is sensitive to the chemical nature and surface morphology of nanoparticles and the specific arrangement of nanoparticles in the ensemble structures, it can be exploited as a unique platform for diverse applications such as chiral sensing and catalysis. Indeed, in recent years, there has been rapid progress in the research of nanoscale chirality both from the experimental and theoretical perspectives. Some of these breakthroughs are highlighted in this special issue. We are grateful to the various leading experts in the field for their contributions to this collection, and excited to share with you the latest advances of nanoscale chirality. We look forward to an even brighter future of the field. Happy reading…… Shaowei Chen received his B.S. degree in Chemistry from the University of Science and Technology of China in 1991, and his M.S. and Ph.D. degrees from Cornell University in 1993 and 1996, respectively. Following a postdoctoral appointment in the University of North Carolina - Chapel Hill, he started his independent career in Southern Illinois University - Carbondale in 1998, and then moved to the University of California - Santa Cruz in 2004. He is currently a Professor of Chemistry and the Faculty Director of the UCSC COSMOS program. His research interests are primarily focused on functional nanomaterials and electrochemical energy technologies. Zhiyong Tang obtained his Bachelor's and Master's degrees from Wuhan University in 1996, and his Ph.D. degree with Professor Erkang Wang in 1999 from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. After six years as a postdoctoral fellow in Swiss Federal Institute of Technology Zurich, Oklahoma State University and University of Michigan, he joined the National Center for Nanoscience and Technology, China, in November 2006 as part of the 100-Talent Program of the Chinese Academy of Sciences, and has been a professor ever since. His research interests are mainly focused on controllable synthesis, property manipulation and practical applications of inorganic nanomaterials. Jianping Xie is currently an Associate Professor at the Department of Chemical & Biomolecular Engineering at National University of Singapore (NUS). He received his B.S. and M.S. in Chemical Engineering from Tsinghua University, China, and his Ph.D. from the Singapore-MIT Alliance (SMA) program. His group is known for the work on engineering subnanometer-sized metal nanoclusters for biomedical and catalytic applications. His recent research interests include noble metal nanoclusters, nanomedicine, and nanocatalysis.

Synthesis of Atom‐Precise Chiral Ag14 Clusters Protected by Penicillamine Ligands

AbstractA pair of atom‐precise chiral silver(I) nanocluster enantiomers (Ag14‐d and Ag14‐l) protected by d‐ and l‐penicillamine ligands is reported. Crystallographic structures reveal that the nanoclusters consist of a S2− template and a chiral Ag14 core stabilized by 12 penicillamine ligands. The penicillamine ligands show two binding fashions: (i) only thiolate coordination, and (ii) thiolate and carboxylate co‐coordination. Meanwhile, the two enantiomers show strong circular dichroism with opposite signals (mirror image relationship) owing to the chiral metallic core induced by chiral ligands, suggesting that the nanoclusters have well‐defined stereostructures as common chiral molecules do. The proton conductivity is also explored due to the existence of both amino groups and carboxylate groups from the penicillamine ligands, which is beneficial to construct H‐bond network for proton transfer.

Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP.

The precise synthesis of polymers derived from alkyl lactate ester acrylates is reported for the first time. Kinetic experiments were conducted to demonstrate that Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) in alcohols at 25 °C provides a green methodology for the LRP of this forgotten class of biobased monomers. The acrylic derivative of ethyl lactate (EL) solvent and homologous structures with methyl and n-butyl ester were polymerized with excellent control over molecular weight, molecular weight distribution, and chain-end functionality. Kinetics plots in conventional alcohols such as ethanol and methanol were first order in the monomer, with molecular weight increasing linearly with conversion. However, aqueous EL mixtures were found to be more suitable than pure EL to mediate the SET-LRP process. The near-quantitative monomer conversion and high bromine chain-end functionality, demonstrated by matrix-assisted laser desorption ionization time-of-flight analysis, further allowed the preparation of innovative biobased block copolymers containing rubbery poly(ethyl lactate acrylate) poly(ELA) sequences. For instance, the poly(ELA)- b-poly(glycerol acrylate) block copolymer self-assembled in water to form stable micelles with chiral lactic acid-derived block-forming micellar core as confirmed by the pyrene-probe-based fluorescence technique. Dynamic light scattering and transmission electron microscopy measurements revealed the nanosize spherical morphology for these biobased aggregates.

The influence of flexible spacer and the chirality of the core on the formation of chiral nematic phase of symmetric dimers containing trifluoromethyl terminal

ABSTRACTSeven symmetric liquid crystal (LC) dimers containing different chiral cores and LC arms have been synthesised, termed EPDA-(R,S)PD, TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD, TFBA-(R)PD, TFBDA-IB and TFBA-IB, respectively. TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD and TFBDA-IB displayed chiral smectic A (SmA*) phase, while EPDA-(R,S)PD, TFBA-(R)PD and TFBA-IB exhibited chiral nematic (N*) phase. The effects of flexible spacer, structural type of LC arms and the chirality of the cores on the thermal properties of the dimers and the formation of N* phase have been studied. The results indicated that the chiral core was prone to induce the N* phase in LC dimer that contained nematic arms although the chirality of the core is very weak, while for the smectic LC arms containing CF3 terminal, the removal of the flexible spacer between chiral core and rigid LC units was conducive to the formation of N* phase. For example, TFBDA-(R)PD and TFBDA-IB displayed SmA* phase, while TFBA-(R)PD and TFBA-IB exhibited N* phase. However TFBA-(R,S)PD did not display N* phase, which reminded us that the chirality of the core and the conformation of the dimer also played an influence in the formation of the LC phase.

Hierarchical MFI Zeolites with a Single-Crystalline Sponge-Like Mesostructure.

Single-crystalline sponge-like MFI mesoporous zeolites (SSMZs) have been synthesized by using bolaform surfactants with an axial chiral binaphthyl core in the hydrophobic tail and triquaternary ammonium head groups, as bifunctional organic structure-directing agents (OSDAs). By changing the length of alkyl chain between a triquaternary ammonium head group and a binaphthyl group from 4 to 10 carbons, SSMZs with high specific surface area (382-434 m2 g-1 ), abundant micropore-mesopore connectivity, and uniform mesopore diameter (4-10 nm) were obtained. OSDAs with an alkyl chain length of 11 and 12 carbons led to the formation of nanorod-constructed mesoporous MFI zeolites. A geometrical matching between the cylindrical arrangement of the binaphthyl groups and the zeolitic framework is speculated to be the key factor for the formation of mesoporous zeolites. The SSMZ zeolites, with abundant mesopores beneficial for the diffusion of reactants, exhibited significantly higher catalytic efficiencies than those of the conventional ZSM-5 with a microcrystal morphology (≈1.5 μm).

Blast response study of the sandwich composite panels with 3D chiral auxetic core

Chiral auxetic cellular structures were fabricated from Ti6Al4V alloy using the Selective Electron Beam Melting method, and tested experimentally under quasi-static and dynamic compression loading conditions. The experimental results were used to validate built computational models of auxetic cellular structure in LS-DYNA. The models were used to study the geometry effect on the Poisson’s ratio of the analysed chiral auxetic structure. The response of sandwich composite panels with auxetic core under blast loading was studied extensively computationally, where the maximum panel displacement and the Specific Energy Absorption (SEA) of the composite panel were evaluated. Three different methods for blast loading (ConWep, Smooth Particle Hydrodynamic, Multi-Material Arbitrary Lagrange-Eulerian) were compared and validated based on the experimental data. It was determined that larger thickness of the cover plate lowers the panel maximum displacement, while the SEA is larger when thinner cover plates are used. Also, it was shown that the chiral unit cell amplitude effect on the maximum displacement and SEA is, in most analysed cases, negligible in comparison to the cell length effect, which is more prominent. The presented study illustrates great potential of using sandwich structures with designed auxetic cellular cores to improve the response of modern composite structures to blast loading.

Effective elastic properties of flexible chiral honeycomb cores including geometrically nonlinear effects

Flexible chiral honeycomb cores generally exhibit nonlinear elastic properties in response to large geometric deformation, which are suited for the design of morphing aerospace structures. However, owing to their complex structure, it is standard to replace the actual core structure with a homogenized core material presenting reasonably equivalent elastic properties in an effort to increase the speed and efficiency of analyzing the mechanical properties of chiral honeycomb sandwich structures. As such, a convenient and efficient method is required to evaluate the effective elastic properties of flexible chiral honeycomb cores under conditions of large deformation. The present work develops an analytical expression for the effective elastic modulus based on a deformable cantilever beam under large deformation. Firstly, Euler–Bernoulli beam theory and micropolar theory are used to analyze the deformation characteristics of chiral honeycombs, and to calculate the effective elastic modulus under small deformation. On that basis, the expression for the effective elastic modulus is improved by including the stretching deformation of the chiral honeycomb structure for a unit cell under conditions of large deformation. The effective elastic moduli calculated by the respective analytical expressions are compared with the results of finite element analysis. The results indicate that the analytical expression obtained under consideration of the geometric nonlinearity is more suitable than the linear expressions for flexible chiral honeycomb cores under conditions of high strain and low elastic modulus.

Reciprocity relations for a conductive scatterer with a chiral core in quasi-static form

We analyse a scattering problem of electromagnetic waves by a bounded chiral conductive obstacle, which is surrounded by a dielectric, via the quasi-stationary approximation for the Maxwell equations. We prove the reciprocity relations for incident plane and spherical electric waves upon the scatterer. Mixed reciprocity relations have also been proved for a plane wave and a spherical wave. In the case of spherical waves, the point sources are located either inside or outside the scatterer. These relations are used to study the inverse scattering problems. doi:10.1017/S144618111800007X

Structurally Precise Dichalcogenolate-Protected Copper and Silver Superatomic Nanoclusters and Their Alloys.

The chalcogenolato silver and copper superatoms are currently a topic of cutting edge research besides the extensively studied Au n(SR) m clusters. Crystal structure analysis is an indispensable tool to gain deep insights into the anatomy of these sub-nanometer clusters. The metal framework and spatial arrangement of the chalcogenolates around the metal core assist in unravelling the structure-property relationships and fundamental mechanisms involved in their fabrication. In this Account, we discuss our contribution toward the development of dichalcogenolato Ag and Cu cluster chemistry covering their fabrication and precise molecular structures. Briefly introducing the significance of the single crystal structures of the atomically precise clusters, the novel dichalcogenolated two-electron superatomic copper and its alloy systems are presented first. The [Cu13{S2CNR}6{C≡CR'}4]+ is so far the first unique copper cluster having Cu13 centered cuboctahedra, which is a miniature of bulk fcc structure. The galvanic exchange of the central Cu with Ag or Au results in a similar anatomy of formed bimetallic [Au/Ag@Cu12(S2CN nBu2)6(C≡CPh)4][CuCl2] species. This is unique in the sense that other contemporary M13 cores in group 11 superatomic chemistry are compact icosahedra. The central doping of Ag or Au significantly affects the physiochemical properties of the bimetallic Cu-rich clusters. It is manifested in the dramatic quantum yield enhancement of the doped species [Au@Cu12(S2CN nBu2)6(C≡CPh)4]+ with a value of 0.59 at 77 K in 2-MeTHF. In the second part, the novel eight-electron dithiophosphate- and diselenophosphate-protected silver systems are presented. A completely different type of architecture was revealed for the first time from the successful structural determination of [Ag21{S2P(O iPr)2}12]+, [Ag20{S2P(O iPr)2}12] and [Au@Ag19{S2P(OPr)2}12]. They exhibit a nonhollow M13 (Ag or AuAg12) icosahedron, capped by 8 and 7 Ag atoms in the former and latter two species, respectively. The overall metal core units are protected by 12 dithiophosphate ligands and the metal-ligand interface structure was found to be quite different from that of Au n(SR) m. Notably, the [Ag20{S2P(O iPr)}12] cluster provides the first structural evidence of a silver superatom with a chiral metallic core. This chirality arises through the simple removal of one of capping Ag+ cations of [Ag21{S2P(O iPr)2}12]+ present on its C3 axis. Further, the effects of the ligand exchange on the structures of [Ag20{Se2P(O iPr)2}12], [Ag21{Se2P(OEt)2}12]+, and [AuAg20{Se2P(OEt)2}12]+ are studied extensively. The structure of the former species is similar to its dithiophosphate counterpart ( C3 symmetry). The latter two ( T symmetry) differ in the arrangement of 8 capping Ag atoms, as they form a cube engraving the Ag13 (AuAg12) icosahedron. The blue shifts in absorption spectra and photoluminescence further indicate the strong influence of the central Au atom in the doped clusters. Finally, the first paradigm of unusual heteroatom doping induced size-structure transformations is discussed by presenting the case of formation of [Au3Ag18{Se2P(O iPr)2}12]+ upon Au doping into [Ag20{Se2P(O iPr)2}12]0. Finally, before concluding this Account, we discuss the possibility of many unique structural isomers with different physical properties for the aforementioned Ag superatoms which need to be explored extensively in the future.

Synthesis of 2,2-Dialkyl Chromanes by Intramolecular Ullmann C-O Coupling Reactions toward the Total Synthesis of D-α-Tocopherol.

The complete synthesis of D-α-tocopherol was achieved using our developed-Ullmann C-O coupling reaction as a key reaction. The synthesis of the core structure of D-α-tocopherol, which is a chiral chromane, has never been reported using intramolecular Ullmann C-O coupling reactions owing to the low reactivity of electron-rich iodoarenes with tertiary alcohols. Because the developed intramolecular C-O coupling reactions prefer electron-rich iodoarenes with tertiary alcohols, we successfully synthesized the chiral chromane core and achieved the total synthesis of D-α-tocopherol.

Mesomorphic properties of non-symmetric three-arm chenodeoxycholic acid-derived liquid crystals

ABSTRACTSix three-arm star-shaped liquid crystals (LCs) based on chenodeoxycholic acid (CDCA), termed as G-BH, G-YD, G-FD, G-DJ, G-DZ and G-BX, respectively, have been synthesised. CDCA was used as the chiral core and the nematic side arm, 6-(4-(ethylbenzoyloxy) phenoxy)-6-oxohexanoic acid, was chosen to be introduced into the two hydroxyl of CDCA to synthesise cholesteric LC (CDCA2EA) and different structures were introduced into the carboxyl group of CDCA to prepare the three-arm star-shaped LCs. Chemical structures and LC properties of the six three-arm LCs were characterised by FTIR, 1H-NMR, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and polarised optical microscopy. G-BH and G-DJ displayed cholesteric phase with a long helical pitch; G-BX displayed nematic phase; and G-YD, G-FD and G-DZ displayed cholesteric phase on heating and on cooling. These results indicated that not only the chiral core CDCA but also the structures of the side arms played an important role in inducing the cholesteric phase of the CDCA-derived LCs. G-DZ displayed selective reflection, a wider ∆λ and red shift on cooling.

Toward Solution Syntheses of the Tetrahedral Au20 Pyramid and Atomically Precise Gold Nanoclusters with Uncoordinated Sites.

A long-standing objective of cluster science is to discover highly stable clusters and to use them as models for catalysts and building blocks for cluster-assembled materials. The discovery of catalytic properties of gold nanoparticles (AuNPs) has stimulated wide interests in gaseous size-selected gold clusters. Ligand-protected AuNPs have also been extensively investigated to probe their size-dependent catalytic and optical properties. However, the need to remove ligands can introduce uncertainties in both the structures and sizes of ligand-protected AuNPs for catalytic applications. Ideal model catalysts should be atomically precise AuNPs with well-defined structures and uncoordinated surface sites as in situ active centers. The tetrahedral ( Td) Au20 pyramidal cluster, discovered to be highly stable in the gas phase, provided a unique opportunity for such an ideal model system. The Td-Au20 consists of four Au(111) faces with all its atoms on the surface. Bulk synthesis of Td-Au20 with appropriate ligands would allow its catalytic and optical properties to be investigated and harnessed. The different types of its surface atoms would allow site-specific chemistry to be exploited. It was hypothesized that if the four corner atoms of Td-Au20 were coordinated by ligands the cluster would still contain 16 uncoordinated surface sites as potential in situ catalytically active centers. Phosphine ligands were deemed to be suitable for the synthesis of Td-Au20 to maintain the integrity of its pyramidal structure. Triphenyl-phosphine-protected Td-Au20 was first observed in solution, and its stability was confirmed both experimentally and theoretically. To enhance the synthetic yield, bidentate diphosphine ligands [(Ph)2P(CH2) nP(Ph)2 or L n] with different chain lengths were explored. It was hypothesized that diphosphine ligands with the right chain length might preferentially coordinate to the Td-Au20. Promising evidence was initially obtained by the formation of the undecagold by the L3 ligand. When the L8 diphosphine ligand was used, a remarkable Au22 nanocluster with eight uncoordinated Au sites, Au22(L8)6, was synthesized. With a tetraphosphine-ligand (PP3), a new Au20 nanocluster, [Au20(PP3)4]Cl4, was isolated with high yield. The crystal structure of the new Au20 core did not reveal the expected pyramid but rather an intrinsically chiral gold core. The surface of the new chiral-Au20 was fully coordinated, and it was found to be highly stable chemically. The Au22(L8)6 nanocluster represents the first and only gold core with uncoordinated gold atoms, providing potentially eight in situ catalytically active sites. The Au22 nanoclusters dispersed on oxide supports were found to catalyze CO oxidation and activate H2 without ligand removal. With further understanding about the formation mechanisms of gold nanoclusters in solution, it is conceivable that Td-Au20 can be eventually synthesized, allowing its novel catalytic and optical properties to be explored. More excitingly, it is possible that a whole family of new atomically precise gold nanoclusters can be created with different phosphine ligands.

Multi-arm azobenzene liquid crystal based on cholic acid: synthesis and mesophase properties

ABSTRACTA new series of multi-arm liquid crystals (D1–D5) based on cholic acid as the chiral core and ω-[4-(p-substituted azobenzeneoxy carbonyl]valeric acid (B1–B5) as the mesogenic arms were designed and synthesised. All the mesogenic arms and the multi-arm liquid crystals were structurally well-characterised using elementary analysis (EA), 1H NMR and FT-IR. The photochemical properties were determined by UV spectra. The optical rotations were measured by Automatic Polarimeter. The phase behaviours were investigated by means of polarised optical microscopy, X-ray diffraction and differential scanning calorimetry, while the effect of the terminal groups of azobenzene on mesogenic and photochemical properties were discussed. The results demonstrated that the mesogenic arms exhibited nematic phase except B3. The multi-arm compounds showed chiral nematic except D3. Cholic acid played an important role in inducing chiral nematic of the multi-arm liquid crystals. Tm or Ti of B1–B5 and D1–D5 are influenced by the effect of electrical effects of the terminal groups and the molecular shapes. Furthermore, the multi-arm compounds exhibited well light sensitivity, owning the photoisomerisation of the tran-form azobenzene to the cis-form azobenzene. λmax of D1–D5 displayed blue shift first and then red shift with the different electrical effects of the terminal groups of mesogenic arms.