Shape-controlled synthesis and self-assembly of hexagonal covellite (CuS) nanoplatelets

Single-crystalline, hexagonal covellite (CuS) nanoplatelets were successfully synthesized through a facile, inexpensive, reproducible, and improved solvothermal process in toluene at 120 degrees C for 24 h with hexadecylamine as a capping agent and copper acetate and carbon disulfide as precursors. These nanoplatelets are about 26+/-1.5 nm in diameter and 8+/-1.2 nm thick, and have a tendency to self-assemble into pillarlike nanostructures with face-to-face stacks, raftlike nanostructures with side-by-side arrays, and stratiform nanostructures with layer-by-layer self-assembly. The crystal shape, morphology, and crystallographic orientation of the covellite obtained were investigated by means of XRD, TEM, and high-resolution TEM, and a potential self-assembly mechanism was proposed.     

Synthesis and photocatalytic properties of Cu2S-Pd4S hybrid nanoplates

Hex appeal! Cu(2)S-Pd(4)S hybrid nanocrystals with a novel hexagonal nanoplate structure were prepared in high yield by a simple one-pot synthetic method (see figure). Successful synthesis of this unique structure was achieved through a consecutive thermolysis process. The Cu(2)S-Pd(4)S hybrid nanoplates exhibited substantially higher photocatalytic activities than pure Cu(2)S nanoplates.     

Transfer, amplification, and inversion of helical chirality mediated by concerted interactions of C3-supramolecular dendrimers

The synthesis, structural, and retrostructural analysis of two libraries containing 16 first and second generation C(3)-symmetric self-assembling dendrimers based on dendrons connected at their apex via trisesters and trisamides of 1,3,5-benzenetricarboxylic acid is reported. A combination of X-ray diffraction and CD/UV analysis methods demonstrated that their C(3)-symmetry modulates different degrees of packing on the periphery of supramolecular structures that are responsible for the formation of chiral helical supramolecular columns and spheres self-organizable in a diversity of three-dimensional (3D) columnar, tetragonal, and cubic lattices. Two of these periodic arrays, a 3D columnar hexagonal superlattice and a 3D columnar simple orthorhombic chiral lattice with P222(1) symmetry, are unprecedented for supramolecular dendrimers. A thermal-reversible inversion of chirality was discovered in helical supramolecular columns. This inversion is induced, on heating, by the change in symmetry from a 3D columnar simple orthorhombic chiral lattice to a 3D columnar hexagonal array and, on cooling, by the change in symmetry from a 2D hexagonal to a 2D centered rectangular lattice, both exhibiting intracolumnar order. A first-order transition from coupled columns with long helical pitch, to weakly or uncorrelated columns with short helical pitch that generates a molecular rotator, was also discovered. The torsion angles of the molecular rotator are proportional to the change in temperature, and this effect is amplified in the case of the C(3)-symmetric trisamide supramolecular dendrimers forming H-bonds along their column. The structural changes reported here can be used to design complex functions based on helical supramolecular dendrimers with different degree of packing on their periphery.     

Axial-bundle phases--new modes of 2D, 3D, and helical columnar self-assembly in liquid crystalline phases of bolaamphiphiles with swallow tail lateral chains

Two series of polyphilic molecules composed of a rigid and linear p-terphenyl core, terminated at both ends with polar glycerol groups capable of hydrogen bonding, and two branched swallow tail-type lateral chains, composed of a fluorinated and a nonfluorinated branch or two fluorinated branches, were synthesized and investigated by differential scanning calorimetry, polarizing microscopy, and X-ray diffraction (XRD) with respect to their self-assembly in thermotropic liquid crystalline (LC) phases. Hexagonal columnar phases were formed by all molecules, at least at the highest temperature. In these phases the columns are composed of a core of aromatic rods and an aliphatic shell. The aromatic rods form bundles which are rotationally averaged and lie parallel to the column long axis. This unique organization is proven by different optical and XRD methods. The aromatic and glycerol groups inside the rod bundles are segregated into alternating segments. Depending on temperature and molecular structure, long-range intercolumnar correlation of this periodicity could take place, leading to a 3D-ordered LC phase with rhombohedral R ?3m symmetry. The bundles are embedded in the matrix of the lateral chains, which is divided into fluoroalkyl- and aliphatic-rich regions. In the 2D columnar phase the fluorinated regions take the form of either straight columns running along the edges of the hexagonal Voronoi cells or, for compounds with a higher degree of fluorination, fuse to a hexagonal honeycomb enclosing the aromatic cores. In the R ?3m phase the fluorine-rich chains are preferentially found along right- and left-handed helices wound around the 3(1) screw axes between the main aromatic columns.     

六边形非化学计量比CuxS纳米片：合成、表征及电化学性质

分别采用乙二醇(EG)和聚乙烯吡咯烷酮(PVP)为溶剂和模板剂,用简单的回流方法合成六角型非化学计量比CuxS纳米片.并用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见近红外光谱仪(UV-Vis)、循环伏安法(CV)对产物进行表征.TEM研究表明样品形貌为纳米六角片.XRD结果表明,随着Cu/S物质的量比的逐渐增加,样品物相从靛铜矿(covellite)CuS逐渐转变为蓝辉铜矿(digenite)Cu1.8S.此外,随着样品组分的变化,其光学和电化学性质均发生显著变化.     

Control of 1D wave versus 2D honeycomb CoIIICdIICuI heterotrimetallic architectures by Delta L-Lambda L diastereoisomerism of L-cysteinatocobalt(III) building units

The reactions of the Delta L and Lambda L isomers of [Co( l-Hcys- N, S)(en) 2] (2+) ( l-H 2cys = l-cysteine) with CuCl in aqueous HCl gave Co (III)Cu (I) dinuclear complexes with the same S-bridged structures, Delta L- 1 and Lambda L- 1. When Delta L- 1 was treated with CdCl 2 in water, a 1D wavelike (Co (III) 2Cd (II)Cu (I)) n polymeric complex ( 2) was produced. On the other hand, similar treatment of Lambda L- 1 led to the formation of a 2D honeycomb-like (Co (III) 3Cd (II) 3Cu (I)) n polymeric complex ( 3), supported by the presence of counter-monoanions.     

Self-repairing complex helical columns generated via kinetically controlled self-assembly of dendronized perylene bisimides

The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-3-PBI, was recently reported to self-assemble in complex helical columns containing tetramers of PBI as basic repeat unit. These tetramers contain a pair of two molecules arranged side-by-side and another pair in the next stratum of the column turned upside-down and rotated around the column axis. Intra- and intertetramer rotation angles and stacking distances are different. At high temperature, (3,4,5)12G1-3-PBI self-assembles via a thermodynamically controlled process in a 2D hexagonal columnar phase while at low temperature in a 3D orthorhombic columnar array via a kinetically controlled process. Here, we report the synthesis and structural analysis, by a combination of differential scanning calorimetry, X-ray and electron diffraction, and solid-state NMR performed at different temperatures, on the supramolecular structures generated by a library of (3,4,5)nG1-3-PBI with n = 14-4. For n = 11-8, the kinetically controlled self-assembly from low temperature changes in a thermodynamically controlled process, while the orthorhombic columnar array for n = 9 and 8 transforms from the thermodynamic product into the kinetic product. The new thermodynamic product at low temperature for n = 9, 8 is a self-repaired helical column with an intra- and intertetramer distance of 3.5 ? forming a 3D monoclinic periodic array via a kinetically controlled self-assembly process. The complex dynamic process leading to this reorganization was elucidated by solid-state NMR and X-ray diffraction. This discovery is important for the field of self-assembly and for the molecular design of supramolecular electronics and solar cell.     

Novel 3D, 2D, and 0D first-row coordination compounds with 4,4'-bipyridine-N,N'-dioxide incorporating sulfur-containing anions

The reaction of M(S2O6) (M = Cu(II), Ni(II), and Co(II)) with 4,4'-bipyridine-N,N'-dioxide (bpdo) results in the formation of novel 3D, 2D, and mononuclear complexes. Complex 1, {[Cu(H2O)(bpdo)2](S2O6)(H2O)}n, is a 2-D wavelike polymer with the Cu(II) ion located on a 2-fold axis and having a distorted square-pyramidal coordination sphere. With Co(II) and Ni(II), 3-D complexes, {[M(bpdo)3](S2O6)(C2H5OH)7}n [M = Co(II) (2), Ni(II) (3)], were obtained. The metal atoms are situated on centers of symmetry and have octahedral environments coordinated to six bpdo molecules. The same reaction in aqueous solution with a metal/ligand ratio of 1:1 results in the formation of mononuclear complexes, {[M(bpdo)(H2O)5](SO4)(H2O)2} [M = Co(II) (4), Ni(II) (5)], accompanied by the decomposition of the dithionate anions S2O6(2-) to sulfate anions SO4(2-).     

Control of self-assembly of a 3-hexen-1,5-diyne derivative: toward soft materials with an aggregation-induced enhancement in emission

The supramolecular architectures of a fluorophore are controlled through the design of a conjugated polycatenar molecule, the self-assembly of which can be addressed toward a columnar liquid-crystalline phase and organogels. Thus, depending on the environmental conditions for self-assembly, compound CA9 organizes into an unprecedented hexagonal columnar mesophase in the condensed state, in which half a molecule constitutes the slice of the column, or into a rectangular mesomorphic-like organization in the presence of apolar solvents such as cyclohexane and dodecane, at a concentration in which fibers form and gelling conditions are fulfilled. In this Col(r)-type arrangement, the organization within the columns depends on the solvent. All of the materials prepared show luminescence, and moreover, a remarkable 3-fold increase in fluorescence intensity was observed in going from the solution to the gel state.     

Reactions of Cu+(1S, 3D) with CH3Cl, CH2ClF, CHClF2, and CClF3

The reactions of gas-phase Cu+(1S) and Cu+(3D) with CH3Cl, CH2ClF, CHClF2, and CClF3 are examined using the drift cell technique at 3.5 Torr. State-specific product channels and overall bimolecular rate constants for depletion of the two Cu+ states are determined using electronic state chromatography. Cu+(1S) participates exclusively in association with all four neutrals, whereas Cl abstraction is the dominant product channel for Cu+(3D). The resulting CuCl+ product subsequently abstracts Cl- in a secondary process. Tertiary reactions are also observed, which include both hydride abstraction (with CH3Cl) and fluoride abstraction (with the fluorinated neutrals). All product channels can be understood in terms of the known thermochemical and quantum mechanical (i.e., spin) requirements. Cu+(1S) is depleted by all four neutrals at 30% to 40% of the ADO rate under these conditions, whereas Cu+(3D) is observed to react at approximately 80% of the ADO rate with CH3Cl, CH2ClF, and CHClF2. Reaction of excited state Cu+ with CClF3 occurs at only 7% of the ADO rate. The behavior of Cu+(3D) is consistent with a mechanism in which formation of CuCl+ occurs exclusively on the triplet surface via a mechanism in which the metal ion must interact exclusively with Cl.     

Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

Conversion of hexagonal Sb2Te3 nanoplates into nanorings driven by growth temperature

We describe a novel route for the conversion of hexagonal Sb(2)Te(3) nanoplates into nanorings driven by growth temperature in a simple solvothermal process. The transmission electron microscopy was employed to investigate systemically the morphology, size, crystallinity, and microstructure of the as-prepared products. The experiments indicated that the growth temperature had a great effect on the morphology of antimony telluride nanostructures. When the experiments were conducted at 200 °C, the hexagonal antimony telluride nanoplates were obtained. However, if the experiments were carried out at higher temperature of 230 °C, the hexagonal antimony telluride nanorings were achieved by dissolution of the inner part with a higher density of defects of the hexagonal nanoplates for the first time. A possible formation mechanism was proposed on the basis of experimental results and analysis. This work may open a new rational route for the synthesis of the hexagonal antimony telluride nanorings, which may have scientific and technological applications in various functional devices.     

Photoluminescence and conductivity of self-assembled pi-pi stacks of perylene bisimide dyes

The self-assembly of a new, highly fluorescent perylene bisimide dye 2 into pi stacks, both in solution and condensed phase, has been studied in detail by NMR spectroscopy, vapor pressure osmometry (VPO), UV/Vis and fluorescence spectroscopy, differential scanning calorimetry (DSC), optical polarizing microscopy (OPM) and X-ray diffraction. The NMR and VPO measurements revealed the formation of extended pi-pi stacks of the dye molecules in solution. The aggregate size determined from VPO and DOSY NMR measurements agree well with that obtained from the concentration and temperature-dependent UV/Vis spectral data by employing the isodesmic model (equal K model). In the condensed state, dye 2 possesses a hexagonal columnar liquid crystalline (LC) phase as confirmed by X-ray diffraction analysis. The columnar stacking of this dye has been further explored by atomic force microscopy (AFM). Well-resolved columnar nanostructures of the compound are observed on graphite surface. A color-tunable luminescence from green to red has been observed upon aggregation which is accompanied by an increase of the fluorescence lifetime and depolarization. The observed absorption properties can be explained in terms of molecular exciton theory. The charge transport properties of dye 2 have been investigated by pulse radiolysis-time resolved microwave conductivity measurements and a 1D charge carrier mobility up to 0.42 cm(2) V(-1) s(-1) is obtained. Considering the promising self-assembly, semiconducting, and luminescence properties of this dye, it might serve as a useful functional material for nano(opto)electronics.     

具有不同柱状结构的苯并菲盘状液晶化合物的合成及自组装

合成了3种含有不同长度烷基链的苯并菲盘状液晶化合物; 通过1H NMR 和 MALDI-TOF MS对其结构进行了表征; 利用差示扫描量热法(DSC)、热台偏光显微镜(POM)和小角X射线散射实验(SAXS)对3种液晶化合物的自组装行为进行了研究. 结果表明, 烷基链的长度对苯并菲盘状液晶化合物自组装结构的影响显著. 柔性链为辛基的苯并菲盘状液晶化合物自组装成六方柱状液晶相; 柔性链为十二烷基的化合物自组装成倾斜柱状液晶相; 而柔性链为十六烷基的化合物则未形成液晶相.     

7-Azaindolyl- and 2,2'-dipyridylamino-functionalized molecular stars with sixfold symmetry: self-assembly, luminescence, and coordination compounds

Two novel star molecules functionalized with 7-azaindolyl and 2,2'-dipyridylamino groups have been synthesized. Both molecules possess a sixfold rotation symmetry. Molecule L1 is based on the hexaphenylbenzene core with the formula of hexa[p-(7-azaindolyl)phenyl]benzene, while molecule L2 is based on the hexakis(biphenyl)benzene core with the formula of hexa[p-(2,2'-dipyridylamino)biphenyl]benzene. Both compounds have been characterized by single-crystal X-ray diffraction analyses. Molecule L1 forms extended two-dimensional layered structure, while L2 forms interpenetrating columnar stacks in the solid state, as revealed by X-ray diffraction analyses. Nanowire structures based on columnar stacks through self-assembly of L2 on a graphite surface were revealed by an STM study. Molecules L1 and L2 are capable of binding to metal ions, resulting in unusual structural motifs. Two Ag(I) complexes with the formulae of [(AgNO(3))(2)(L1)] (1) and [(AgNO(3))(3)(L1)] (2) were isolated from the reactions of AgNO(3) with L1. Compound 1 displays extended intermolecular pi-pi stacking interactions that are responsible for its extended two-dimensional structure in the crystal lattice. Complex 2 has a "bowl" shape and forms polar stacks in the crystal lattice. A Cu(II) complex with the formula of [{Cu(NO(3))(2)}(6)(L 2)] (3) was isolated from the reaction of Cu(NO(3))(2) with compound L2. The six Cu(II) ions in 3 are chelated by the 2,2'-dipyridylamino groups of the star ligand L2. Intermolecular Cu-O (nitrate) bonds lead to the formation of an extended two-dimensional coordination network of 3. Both L1 and L2 are blue luminescent. Their interactions with Ag(I) or Cu(II) cause drastic quenching of emission. In addition, the luminescence of L1 and L2 is sensitive to the presence of protons, which cause a reduction of emission intensity and a red shift of the emission energy.     

Graphene‐Assisted Room‐Temperature Synthesis of 2D Nanostructured Hybrid Electrode Materials: Dramatic Acceleration of the Formation Rate of 2D Metal Oxide Nanoplates Induced by Reduced Graphene Oxide Nanosheets

A new prompt room temperature synthetic route to 2D nanostructured metal oxide–graphene‐hybrid electrode materials can be developed by the application of colloidal reduced graphene oxide (RGO) nanosheets as an efficient reaction accelerator for the synthesis of δ‐MnO₂ 2D nanoplates. Whereas the synthesis of the 2D nanostructured δ‐MnO₂ at room temperature requires treating divalent manganese compounds with persulfate ions for at least 24 h, the addition of RGO nanosheet causes a dramatic shortening of synthesis time to 1 h, underscoring its effectiveness for the promotion of the formation of 2D nanostructured metal oxide. To the best of our knowledge, this is the first example of the accelerated synthesis of 2D nanostructured hybrid material induced by the RGO nanosheets. The observed acceleration of nanoplate formation upon the addition of RGO nanosheets is attributable to the enhancement of the oxidizing power of persulfate ions, the increase of the solubility of precursor MnCO₃, and the promoted crystal growth of δ‐MnO₂ 2D nanoplates. The resulting hybridization between RGO nanosheets and δ‐MnO₂ nanoplates is quite powerful not only in increasing the surface area of manganese oxide nanoplate but also in enhancing its electrochemical activity. Of prime importance is that the present δ‐MnO₂–RGO nanocomposites show much superior electrode performance over most of 2D nanostructured manganate systems including a similar porous assembly of RGO and layered MnO₂ nanosheets. This result underscores that the present RGO‐assisted solution‐based synthesis can provide a prompt and scalable method to produce nanostructured hybrid electrode materials.     

Facile synthesis of 3D hierarchical foldaway-lantern-like LiMnPO4 by nanoplate self-assembly, and electrochemical performance for Li-ion batteries

Olivine-structured LiMnPO(4) with 3D foldaway-lantern-like hierarchical structures have been prepared via a one-step, template-free, solvothermal approach in ethylene glycol. The foldaway-lantern-like LiMnPO(4) microstructures are composed of numerous nanoplates with thickness of about 20 nm. A series of electron microscopy characterization results indicate that the obtained primary LiMnPO(4) nanoplates are single crystalline in nature, growing along the [010] direction in the (100) plane. Time-dependent morphology evolution suggests that ethylene glycol plays dual roles in oriented growth and self-assembly of such unique structures. After carbon coating, the as-prepared LiMnPO(4) cathode demonstrated a flat potential at 4.1 V versus Li/Li(+) with a specific capacity close to 130 mA h g(-1) at 0.1 C, along with excellent cycling stability.     

Atomistic simulations of 2D bicomponent self-assembly: from molecular recognition to self-healing

Supramolecular two-dimensional engineering epitomizes the design of complex molecular architectures through recognition events in multicomponent self-assembly. Despite being the subject of in-depth experimental studies, such articulated phenomena have not been yet elucidated in time and space with atomic precision. Here we use atomistic molecular dynamics to simulate the recognition of complementary hydrogen-bonding modules forming 2D porous networks on graphite. We describe the transition path from the melt to the crystalline hexagonal phase and show that self-assembly proceeds through a series of intermediate states featuring a plethora of polygonal types. Finally, we design a novel bicomponent system possessing kinetically improved self-healing ability in silico, thus demonstrating that a priori engineering of 2D self-assembly is possible.     

Formation Mechanism of Mesostructured Silica in Confined Space: An In Situ GISAXS Study

The structural evolution of periodic mesoporous material within the channels of anodic alumina membranes (AAMs) by evaporation‐induced self‐assembly (EISA) is investigated by a combination of in situ grazing‐incidence small‐angle X‐ray scattering (GISAXS) with parallel detection of solvent evaporation and ex situ transmission electron microscopy (TEM). Kinetically controlled and equilibrium‐controlled structural evolution can be distinguished for these EISA processes. A new mechanism for formation of mesostructures in the confined environment of AAMs is proposed. Data are presented for samples synthesized with nonionic surfactants at various surfactant:silica ratios and relative humidities. The formation of and transformations between circular or columnar 2D hexagonal and tubular lamellar structures are observed. The circular hexagonal phase is kinetically favored over the columnar hexagonal orientation. The TEM images provide evidence that phase transformations, depending on their type, either start preferentially at the channel wall or in the center of the mesostructured fibers.     

Morphology control and 2D self-assembly of poly(styrene-co-divinylbenzene) capsules

In this paper, monodisperse poly(styrene-co-divinylbenzene) (PS-DVB) capsules with a bowl-like morphology were prepared controllably by regulating the content of DVB and dispersant. Using as-prepared PS-DVB capsules as building blocks, two-dimensional (2D) uniform hexagonal close-packed array with same orientation of each bowl was successfully fabricated by solvent evaporation. The size distribution showed that the capsules were still spherical in acetone before assembly and thus certified that the capsules caved in after self-assembly. Many factors including DVB content in capsules, experimental temperature and dispersants play important roles on regularity of orientation. Besides, "local self-assembly" array using multi-caved capsule as building blocks was obtained. More study proceeds with it, further advanced materials with complex functionalities or peculiar behavior could be expected.