Linear nanostructure formation of aldehydes by self-directed growth on hydrogen-terminated silicon(100)

The self-directed growth of organic molecules on silicon surfaces allows for the rapid, parallel production of hybrid organic-silicon nanostructures. In this work, the formation of benzaldehyde- and acetaldehyde-derived nanostructures on hydrogen-terminated H-Si(100)-2x1 surface is studied by scanning tunneling microscopy in ultrahigh vacuum and by quantum mechanical methods. The reaction is a radical-mediated process that binds the aldehydes, through a strong Si-O covalent bond, to the surface. The aldehyde nanostructures are generally composed of double lines of molecules. Two mechanisms that lead to double line growth are elucidated.     

Surface modification of self-assembled one-dimensional organic structures: white-light emission and beyond

Surface modification is an important method to functionalize micro-/nanostructures, but substrates are mainly confined to robust inorganic compounds. We develop here a facile method to modify the surface of a fragile organic 1D microstructure. The bulk molecules and surface modifier were designed with orthogonal solubility to protect the molecular crystals from destruction under the reaction conditions. As a proof of concept, white-light-emitting 1D microstructures were obtained by grafting red chromophores onto the surface of self-assembled blue-emissive microwires via a heterophase S(N)2 reaction. Spatial distribution of the two species is visualized by fluorescent lifetime mapping, which reveals a core-shell structure. The ability to postfunctionalize organic 1D structures enables many applications, where the surface property plays key roles, such as an organic P-N junction and a biosensor.     

Molybdenum trioxide nanostructures: the evolution from helical nanosheets to crosslike nanoflowers to nanobelts

MoO(3) nanostructures with different morphologies, such as helical nanosheets, crosslike nanoflowers, and nanobelts, have been synthesized on a large scale by an environmentally friendly chemical route. The evolution process from helical nanosheets to crosslike nanoflowers to nanobelts is observed for the first time. The influences of reaction time and the molar ratio of molybdenum and H(2)O(2) on the morphologies of MoO(3) nanostructures have been investigated. The synthetic process is environmentally friendly and may be extended to synthesize nanostructures of other metal (W, Ti, and Cr) oxides.     

Synthesis of two mirror image 4-helix junctions derived from glycerol nucleic acid

Structural DNA nanotechnology relies on Watson-Crick base pairing rules to assemble DNA motifs into diverse arrangements of geometric shapes and patterns. While substantial effort has been devoted to expanding the programmability of natural DNA, considerably less attention has been given to the development of nucleic acid structures based on non-natural DNA polymers. Here we describe the use of glycerol nucleic acid (GNA), a simple polymer based on an acyclic repeating unit, as an alternative genetic material for assembling nucleic acid nanostructures independent of RNA or DNA recognition. We synthesized two 4-helix junctions based entirely on GNA self-pairing and showed that GNA provides easy access to highly stable nanostructures with left- and right-handed helical configurations.     

Clean coupling of unfunctionalized porphyrins at surfaces to give highly oriented organometallic oligomers

The direct coupling of complex, functional organic molecules at a surface is one of the outstanding challenges in the road map to future molecular devices. Equally demanding is to meet this challenge without recourse to additional functionalization of the molecular building blocks and via clean surface reactions that leave no surface contamination. Here, we demonstrate the directional coupling of unfunctionalized porphyrin molecules--large aromatic multifunctional building blocks--on a single crystal copper surface, which generates highly oriented one-dimensional organometallic macromolecular nanostructures (wires) in a reaction which generates gaseous hydrogen as the only byproduct. In situ scanning tunneling microscopy and temperature programmed desorption, supported by theoretical modeling, reveal that the process is driven by C-H bond scission and the incorporation of copper atoms in between the organic components to form a very stable organocopper oligomer comprising organometallic edge-to-edge porphyrin-Cu-porphyrin connections on the surface that are unprecedented in solution chemistry. The hydrogen generated during the reaction leaves the surface and, therefore, produces no surface contamination. A remarkable feature of the wires is their stability at high temperatures (up to 670 K) and their preference for 1D growth along a prescribed crystallographic direction of the surface. The on-surface formation of directional organometallic wires that link highly functional porphyrin cores via direct C-Cu-C bonds in a single-step synthesis is a new development in surface-based molecular systems and provides a versatile approach to create functional organic nanostructures at surfaces.     

Ag(111)表面Ag配位结构的分等级组装

表面辅助的金属有机纳米结构因其结构稳定性和潜在应用受到广泛关注。在金属有机纳米结构中,金属原子来源于外部沉积的金属或金属表面原子。外部沉积的金属原子种类多样,取决于目标纳米结构。然而,金属表面原子受限于表面科学常用的金、银和铜单晶金属表面。金属有机纳米结构大多包括Au配位或是Cu配位结构,而只有少量的用表面Ag原子构成。分子金属相互作用的进一步研究有助于预期纳米结构的精确控制形成。至于构建基元,有机分子通过M―C、M―N和M―O键与表面金属原子配位。末端炔反应或者乌尔曼耦合能够实现C―M―C节点的形成。Cu和Au原子能够与含有末端氰基或吡啶基官能团的分子配位形成N―M―N键。另外,表面Ag增原子能够通过Ag―N配位键与酞菁分子配位。然而,M―O配位键的相关研究较少。因此,我们计划使用末端羟基分子与Ag增原子配位形成金属有机配位纳米结构去研究O―Ag节点。我们通过扫描隧道显微镜利用4, 4’-二羟基-1, 1’: 3’, 1’’-三联苯分子(4, 4’-dihydroxy-1, 1’: 3’, 1’’-terphenyl,H3PH)和Ag增原子成功构筑了一系列二维有序纳米结构。在室温下,蒸镀的H3PH分子自组装形成由环氢键连接的密堆积结构。当退火温度提升到330 K,一种新的纳米结构出现了,该结构由O―Ag配位键和氢键共同作用形成。进一步地提升退火温度至420 K,蜂巢结构和共存的二重配位链出现,这两种结构中仅由O―Ag―O键构成。为分析金属分子反应路径和O―Ag―O键的能量势垒,我们对该体系进行密度泛函理论计算。计算结果显示,O―Ag键形成的能量势垒是1.41 eV,小于O―Ag―O节点1.85 eV的能量势垒。这也解释了分等级金属-有机纳米结构形成的原因。我们的实验结果提供了一种利用有机小分子和金属增原子来设计和构筑分等级二维纳米结构的有效方法。     

Controlled fabrication of one-dimensional polymer nanostructures via metallogel template polymerization

A facile method is reported to controllably fabricate one dimensional(1D) polymer nanostructures via metallogel template polymerization.The metallogel was prepared through coordination interactions between silver ions and a ligand(L) bearing three pyridyl groups in tetrahydrofuran(THF).The diameters of the metallogel nanofibers could be tuned by the gel concentration(GC).Due to its high thermal stability and facility of removal,the metallogel was used as the template for radical polymerization of diacryolyl-2,6-diaminopyridine(DADAP) to form poly-diacryolyl-2,6-diaminopyridine(PDADAP) nanostructures.The gradually eroding of the templates by PDADAP provided us an effective way to fabricate various nanostructures of the polymer.We have demonstrated that different 1D nanostructures,including nanoribbons,nanotubes and nanowires,could be selectively fabricated by adjusting polymerization time,monomer concentration and GC.The rheological properties of the gel samples were tested by a rheometer.As prolonging the reaction time,more and more polymers were formed and the strength of the resulting polymer gels became higher and higher.The simple preparation process,easy controlled microstructures and adequate gel strength would make it a facile synthetic method for different 1D polymer nanosturctures.     

Room-temperature surface-erosion route to ZnO nanorod arrays and urchin-like assemblies

A solution surface-erosion route was successfully employed to produce one-dimensional (1D) ZnO nanostructures. ZnO nanorod arrays and three-dimensional urchin-like assemblies could be selectively obtained with different manipulations. In this process, zinc foil was introduced to an organic solution system and acted both as a reactant and substrate to support the 1D nanostructures obtained. This method, without any template, apparatus, surfactants, or additional heterogenous substrates, has greatly simplified the preparation of oriented 1D ZnO nanostructures. In particular, this simple route could be carried out at room temperature over a period as short as several minutes, thus it could be conveniently transferred to industrial applications. The possible formation mechanism, erosion process, and influence factors were also investigated.     

Encoded Helical Self-Organization and Self-Assembly into Helical Fibers of an Oligoheterocyclic Pyridine - Pyridazine Molecular Strand

The conformational information of an oligoheterocyclic strand containing a repeating pyridine - pyridazine codon self-organizes into a helical molecular unit, which subsequently self-assembles into helical fibers and macrofibers in dichloromethane and pyridine. The spontaneous formation of helical structures is based on a general self-organization process enforced by the conformational information encoded within the molecular strand itself.     

Synthesis of tri-, hexa-, and nonasaccharide subunits of the atypical O-antigen polysaccharide of the lipopolysaccharide from Danish Helicobacter pylori strains

Synthesis of trisaccharide repeating unit, -->3)-alpha-D-Rhap-(1-->2)-alpha-D-Manp3CMe-(1-->3)-alpha-L-Rha p-(1-->, and its dimeric hexa- and trimeric nonasaccharide subunits of the atypical O-antigen polysaccharide of the lipopolysaccharide from Danish H. pylori strains D1, D3, and D6 has been accomplished. Successful synthesis of the hexasaccharide and the nonasaccharide was possible by dimerization and trimerization of the suitably protected trisaccharide repeating unit, in which three monosaccharide moieties were arranged in a proper order by placing the sterically demanding 3-C-methyl-D-mannose moiety in between D- and L-rhamnoses. Key steps include the coupling of three monosaccharide moieties and dimerization and trimerization of the trisaccharide unit by glycosylations employing the 2'-carboxybenzyl glycoside method. Also presented is a method for the synthesis of the novel branched sugar, 3-C-methyl-D-mannose moiety by elaboration of its equatorial hydroxyl and axial methyl groups at C-3' in the disaccharide stage.     

Controllable Macroscopic Chirality of Coordination Polymers through pH and Anion-Mediated Weak Interactions

Helical architectures with controllable helical sense bias have recently attracted considerable interest for mimicking biological helices and developing novel chiral materials. Coordination polymers (CPs), composed of metal ion nodes and organic linkers, are intriguing systems showing tunable structures and functions. However, CPs with helical morphologies have rarely been explored so far. Particularly, chirality inversion through external stimulus has not been achieved in helical CPs. In this work, we carried out an in-depth investigation on the self-assembly of 1D gadolinium(III) phosphonate CPs using GdX₃ (X=Cl, Br, I) and Gd(RSO₃) (R=CH₃, C₆H₅, CF₃) as metal sources and R-(1-phenylethylamino)methyl phosphonic acid (R-pempH₂) as ligand. Superhelices were formed by precise control of the interchain interactions through different intercalated anions. Furthermore, the twisting direction of superhelices could be controlled by synergistic effect of anions and pH. This study may provide a new route to fabricate helical nanostructures of CPs with a desirable chiral sense and help understand the inner mechanism of the self-assembly process of macroscopic helical structures of molecular systems.     

Glycyrrhizic acid based self-assembled helical nanostructures as scaffolds for asymmetric Diels-Alder reaction

Glycyrrhizic acid (GA), as a traditional herbal, can self-assemble into helical nanofiber in the water. The formed helical nanostructures can be employed as scaffolds for asymmetric Diels-Alder reaction.     

Assembly of an Achiral Chromophore into Light‐Responsive Helical Nanostructures in the Absence of Chiral Components

The chirality found in living organisms is one of unsolved mysteries on Earth. It is crucial to understand the manner in which small achiral molecules evolve into helical superstructures in the absence of chiral components because this process can provide important insights regarding the origin of chirality in nature. 1) the uncommon helical assembly of an achiral trigonal chromophore into helical nanostructures with aggregation‐induced emission enhancement (AIEE) characteristics and 2) the tunability of the helical pitch and fluorescence intensity in response to light is reported. The Rietveld refinement of X‐ray diffraction (XRD) patterns and the growth process suggest that a striking transformation from an achiral to an asymmetric molecule can occur as a result of specific interactions with certain solvents, presumably leading to the unique helical assembly. More importantly, exposure to UV or visible light promoted not only the formation of irregular helical structures with a wide range of pitch lengths but also an increase in fluorescence intensity.     

Interfacial Organization of Y‐Shaped Rod–Coil Molecules Packed into Cylindrical Nanoarchitectures

The behavior at the air/water interface and the structures of Langmuir–Blodgett monolayers at different surface pressures of rod–coil molecules, which consist of a Y‐shaped rigid aromatic segment containing peripheral tetradecyloxy groups and a flexible poly(ethylene oxide) (PEO) chain with 17, 21, 34, or 45 repeating ethylene oxide units (Y17, Y21, Y34, and Y45), were investigated. For the Y21 and Y34 molecules, AFM images revealed two kinds of cylindrical nanoarchitectures formed upon compression. The nanostructured films were further investigated by UV/Vis and FTIR spectroscopy. The formation of the cylindrical nanoarchitectures was due to different tilting angles offered by the mismatch of the cross‐sectional areas of the PEO chain and the benzene ring with attached alkyl chains, and the different PEO contents of the molecules. The multiple π–π stacking and hydrophobic interactions provide exceptional stability of the nanostructures and allow them to be preserved in the course of flipping. For the shortest PEO chain of the Y17 molecule, spontaneous aggregation occurred. The Y45 molecule revealed the formation of 2D circular domains caused by entanglement of the longest PEO chains and coiling at the air/water interface. In addition, an interesting vortical morphology was obtained for the Y21 molecule upon deposition of the film onto a mica substrate, which indicates that the substrate chemistry also has an effect on the morphologies during the film‐transfer process.     

Synthesis of chiral polybinaphthyls with novel conjugated chromophores

An efficient strategy has been developed to incorporate new chromophores into chiral binaphthyl polymers. The repeating units of these polymers are made of conjugated structures with strongly electron-donating amino groups at the both ends. These optically active materials contain the highest possible density of chromophores in a polymer chain since every repeating unit in these polymers is a chromophore. They are soluble in common organic solvents and can be easily processed. The spectroscopic properties of these polymers are studied. The structural similarity of the chromophores in these chiral conjugated polymers with those of two-photon absorbing molecules may lead to interesting optical properties.     

The Formation of Organogels and Helical Nanofibers from Simple Organic Salts

Simple organic salts based on aniline‐derived cations and D ‐tartrate anions formed organogels and helical nanofibers. The organic salt (p‐fluoroanilinium)(D ‐tartrate) was found to generate an organogel despite the absence of a hydrophobic alkyl chain, whereas (p‐iodoanilinium)(D ‐tartrate) formed helical nanofibers in braided ropelike structures through a rolling‐up process. The helicity of these nanofibers could be reversed by changing the growth solvent. The driving forces responsible for the formation of the nanofibers were determined to be 1D O?H???O^? hydrogen‐bonding interactions between D ‐tartrate anions and π stacking of anilinium cations, as well as steric hindrance between the hydrogen‐bonded chains.     

Unprecedented diverse nanostructures formed by amphiphilic graft copolymer bearing PEO side chains synthesized by ATNRC

A series of well‐defined amphiphilic graft copolymers bearing hydrophilic poly(ethylene oxide) (PEO) side chains with tunable grafting densities were synthesized by atom transfer nitroxide radical coupling (ATNRC) reaction using CuBr/PMDETA as catalytic system via the grafting‐onto strategy. PEO side chains were linked to α‐C of carbonyl of polyacrylate‐based backbone, not to the ester side groups as usual, so that every repeating unit of the backbone possessed a pendant steric bulky tert‐butyl group. The critical micelle concentrations of the obtained amphiphilic graft copolymers in aqueous media determined by fluorescence probe technique using pyrene as probe increased with the raising of molecular weights. These amphiphilic graft copolymers with novel chemical structure showed unprecedented diverse nanostructures visualized by transmission electron microscopy in aqueous media and micellar morphologies varied with the changing of experiment parameters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Conformational effect of 2,6-bis(imidazol-1-yl)pyridine on the self-assembly of 1D coordination chains: spontaneous resolution, supramolecular isomerism, and structural transformation

The achiral 2,6-bis(imidazol-1-yl)pyridine (L) was used as the ditopic organic tecton for the formation of coordination polymers with Zn(II) ions. Hydrothermal reaction between L and ZnX2 (X=Br, Cl) afforded spontaneous resolved double helical motifs in ZnLCl2.0.5H2O (1) and ZnLBr2.0.25H2O (2). In the homochiral crystals of 1a and 2a, the helices are of M-helicity, whereas, in 1b and 2b, they are of P-helicity. In contrast, solvothermal reaction between L and ZnCl2 in dried DMF afforded achiral ZnLCl2 (3a), which exhibits a zigzag polymeric motif. An achiral polymorph 3b which contains 21 helical chains was obtained in wet DMF. The formation of different 1D motifs was related to the conformations of L. All these compounds were characterized by infrared spectroscopy, elemental analyses, and single-crystal X-ray diffraction. As revealed by thermal gravimetric analysis and powder X-ray diffraction study, the homochiral motif in 1 was stable even upon removal of guest water molecules. Contrastingly, structural transformation from 3a or 3b to 1 is possible upon hydration.     

Strain‐Induced Isomerization in One‐Dimensional Metal–Organic Chains

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution‐ and solid‐phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom‐up on‐surface synthesis of well‐defined nanostructures. We report an internal strain‐induced skeletal rearrangement of one‐dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu‐catalyzed debromination of organic monomers to generate 1,5‐dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond‐resolved non‐contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate‐induced internal strain drives the skeletal rearrangement of MOCs via 1,3‐H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain‐induced structural rearrangement in 1D systems will enrich the toolbox for on‐surface synthesis of novel functional materials and quantum nanostructures.     

Functionalizing Designer DNA Crystals with a Triple‐Helical Veneer

DNA is a very useful molecule for the programmed self‐assembly of 2D and 3D nanoscale objects. 1 The design of these structures exploits Watson–Crick hybridization and strand exchange to stitch linear duplexes into finite assemblies. 2 – 4 The dimensions of these complexes can be increased by over five orders of magnitude through self‐assembly of cohesive single‐stranded segments (sticky ends). 5 , 6 Methods that exploit the sequence addressability of DNA nanostructures will enable the programmable positioning of components in 2D and 3D space, offering applications such as the organization of nanoelectronics, 7 the direction of biological cascades, 8 and the structure determination of periodically positioned molecules by X‐ray diffraction. 9 To this end we present a macroscopic 3D crystal based on the 3‐fold rotationally symmetric tensegrity triangle 3 , 6 that can be functionalized by a triplex‐forming oligonucleotide on each of its helical edges.