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1.
Diarylethene Self‐Assembled Monolayers: Cocrystallization and Mixing‐Induced Cooperativity Highlighted by Scanning Tunneling Microscopy at the Liquid/Solid Interface 下载免费PDF全文
Dr. Denis Frath Dr. Takeshi Sakano Yohei Imaizumi Soichi Yokoyama Dr. Takashi Hirose Prof. Kenji Matsuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11350-11358
Stimulus control over 2D multicomponent molecular ordering on surfaces is a key technique for realizing advanced materials with stimuli‐responsive surface properties. The formation of 2D molecular ordering along with photoisomerization was monitored by scanning tunneling microscopy at the octanoic acid/highly oriented pyrolytic graphite interface for a synthesized amide‐containing diarylethene, which underwent photoisomerization between the open‐ and closed‐ring isomers and also a side‐reaction to give the annulated isomer. The nucleation (Kn) and elongation (Ke) equilibrium constants were determined by analysis of the concentration dependence of the surface coverage by using a cooperative model at the liquid/solid interface. It was found that the annulated isomer has a very large equilibrium constant, which explains the predominantly observed ordering of the annulated isomer. It was also found that the presence of the closed‐ring isomer induces cooperativity into the formation of molecular ordering composed of the open‐ring isomer. A quantitative analysis of the formation of ordering by using the cooperative model has provided a new view of the formation of 2D multicomponent molecular ordering. 相似文献
2.
Nanostructuring of Self‐Assembled Porphyrin Networks at a Solid/Liquid Interface: Local Manipulation under Global Control 下载免费PDF全文
Dr. Michiel J. J. Coenen Dr. Tony Khoury Prof. Maxwell J. Crossley Dr. Bas L. M. Hendriksen Dr. Johannes A. A. W. Elemans Prof. Sylvia Speller 《Chemphyschem》2014,15(16):3484-3488
Molecules of (5,10,15,20‐tetraundecylporphyrinato)‐copper(II) [(TUP)Cu] can self‐assemble into four different polymorphs at the interface between highly oriented pyrolytic graphite and 1‐octanoic acid. Scanning tunneling microscopy (STM) reveals that it is possible to combine the global control over monolayer structure, provided by the composition and concentration of the supernatant solution, with local control, from nanomanipulation by the STM tip. In the initially formed monolayer, with a polymorph composition governed by the concentration of (TUP)Cu in the supernatant solution, the exchange of molecules physisorbed at the solid/liquid interface with those in the liquid is very limited. By using a nanoshaving procedure at the tip, defects are created in the monolayer, and these serve as local manipulation sites to create domains of higher or lower molecular density, and to incorporate a second molecular species, (TUP)Co into the monolayer of (TUP)Cu. 相似文献
3.
Takeshi Sakano Dr. Jun‐ya Hasegawa Dr. Kenji Higashiguchi Prof. Kenji Matsuda 《化学:亚洲杂志》2012,7(2):394-399
The self‐assembled structure of alkoxy‐ and N‐alkylcarbamoyl‐substituted zinc–tetraphenylporphyrin at the liquid–highly oriented pyrolytic graphite (HOPG) interface was observed by using scanning tunneling microscopy. The alkoxy porphyrin showed a phase transition from face‐on to edge‐on ordering. The phase transition requires the close‐packed structure of alkoxy porphyrin. The chronological change of the ordering was traced to show the existence of several types of Ostwald ripening including two‐step phase transition from small edge‐on to face‐on and then further to edge‐on orderings. On the other hand, the N‐alkylcarbamoyl porphyrin showed persistent edge‐on ordering, and the ordering was analyzed by the Moiré pattern. Although the edge‐on ordering is observed only in the nonpolar solvent, the orderings have potential applications in the charge and energy transfer. 相似文献
4.
Frontispiece: Diarylethene Self‐Assembled Monolayers: Cocrystallization and Mixing‐Induced Cooperativity Highlighted by Scanning Tunneling Microscopy at the Liquid/Solid Interface 下载免费PDF全文
Dr. Denis Frath Dr. Takeshi Sakano Yohei Imaizumi Soichi Yokoyama Dr. Takashi Hirose Prof. Kenji Matsuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32)
5.
Javier Saiz‐Poseu Dr. Jordi Faraudo Antoni Figueras Dr. Ramon Alibes Dr. Felix Busqué Dr. Daniel Ruiz‐Molina 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):3056-3063
The large tendency of catechol rings to adsorb on surfaces has been studied by STM experiments with molecular resolution combined with molecular‐dynamics simulations. The strong adhesion is due to interactions with the surface and solvent effects. Moreover, the thermodynamic control over the differential adsorption of 1 and the nonanoic solvent molecules has been used to induce a new temperature‐induced switchable interconversion. Two different phases that differ in their crystal packing and the presence of solvent molecules coexist upon an increase or decrease in the temperature. These results open new insight into the behavior of catechol molecules on surfaces and 2D molecular suprastructures. 相似文献
6.
Peisi Keg Anup Lohani Denis Fichou Yeng Ming Lam Yiliang Wu Beng S. Ong Subodh G. Mhaisalkar 《Macromolecular rapid communications》2008,29(14):1197-1202
A solution processible polymer—poly(3,3‴‐didodecylquaterthiophene) (PQT‐12) is investigated at the liquid/solid interface using the scanning tunneling microscopy (STM). Two‐dimensional ordered films made up of self‐assembled domains, with dimensions of 100 nm × 50 nm adsorbed on highly oriented pyrolytic graphite (HOPG) were formed. These domains consist of parallel lamellar polymer chains, with the alkyl chains forming interdigitated structures, along with U‐shaped and closed ring segments of the polymer chains. A polymer chain packing model is proposed herein, which attempts to propose a correlation between the packing of long chains and charge mobilities. These STM results could help in understanding the relationship between the extended conjugation and molecular organization of the PQT‐12 chains.
7.
Dr. Ayuk M. Ako Dr. Mohammad Sahabul Alam Mostafizur Rahman Dr. Jonathan P. Hill Dr. Noelia M. Sanchez‐Ballester Dr. Katsuhiko Ariga Dr. Gernot Buth Dr. Christopher E. Anson Prof. Dr. Annie K. Powell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16419-16425
The synthesis and structures of the N‐[(2‐hydroxy‐3‐methyl‐5‐dodecylphenyl)methyl]‐N‐(carboxymethyl)glycine disodium salt (H L ) ligand and its neutral mononuclear complex [FeIII( L )(EtOH)2] ( 1 ) are reported. Structural and electronic properties of 1 were investigated by using scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy (CITS) techniques. These studies reveal that molecules of 1 form well‐ordered self‐assemblies when deposited on a highly oriented pyrolytic graphite (HOPG) surface. At low concentrations, single or double chains (i.e., nanowires) of the complex were observed, whereas at high concentration the complex forms crystals and densely packed one‐dimensional structures. In STM topographies, the dimensions of assemblies of 1 found on the surface are consistent with dimensions obtained from X‐ray crystallography, which indicates the strong similarities between the crystal form and surface assembled states. Double chains are attributed to hydrogen‐bonding interactions and the molecules align preferentially along graphite defects. In the CITS image of complex 1 a strong tunneling current contrast at the positions of the metal ions was observed. These data were interpreted and reveal that the bonds coordinating the metal ions are weaker than those of the surrounding ligands; therefore the energy levels next to the Fermi energy of the molecule should be dominated by metal‐ion orbitals. 相似文献
8.
Giuseppina Pace Dr. Artur Stefankiewicz Jack Harrowfield Prof. Jean‐Marie Lehn Prof. Paolo Samorì Prof. 《Chemphyschem》2009,10(4):699-705
On edge : Self‐assembled monolayers of a bis(hydrazone)‐based molecular grid physisorbed on graphite are studied by scanning tunneling microscopy (see picture). High order is attained at the supramolecular level by thermal annealing of the grid‐based films. A preferential edge‐on configuration of the molecular grid with respect to the substrate is found.
9.
Dr. Hélène Bertrand Dr. Régis Guillot Dr. Marie‐Paule Teulade‐Fichou Dr. Denis Fichou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14654-14664
A series of 5,11,17‐triazatrinaphthylene (TrisK) derivatives, large disk‐like π‐conjugated molecules with C3h symmetry, has been synthesised by following an optimised synthetic pathway. The synthesis was performed by a four‐step protocol based on the N‐arylation of 1,3,5‐tribromobenzene with appropriate anthranilate derivatives. This strategy permits the generation of either chlorinated ( TrisK‐Cl‐OCn ) or non‐chlorinated ( TrisK‐H‐OCn ) alkoxy‐substituted derivatives (OCnH2n+1 with n=3, 10, 12 and 16), thus providing additional versatility in the control of the structure–property relationships. The electronic properties of the various TrisK compounds have been characterised in solution by absorption and emission spectroscopies as well as cyclic voltammetry. The crystal structure of 2,8,14‐propyloxy‐5,11,17‐triazatrinaphthylene TrisK‐H‐OC3 has been determined by X‐ray diffraction analysis, which revealed the presence of stabilising weak intermolecular H bonds. Scanning tunnelling microscopy (STM) at the liquid/solid interface has revealed the remarkable 2D self‐assembling properties of the TrisK compounds. In particular, it has shown that TrisK‐H‐OC12 forms three concomitant self‐organised 2D phases with different row‐packing arrangements. This 2D polymorphism arises from slow ordering due to the presence of three long dodecyloxy chains on the molecular backbone. Individual molecules can be imaged with spectacular intramolecular resolution, thus providing the possibility of correlating the STM features with the calculated charge density distribution. 相似文献
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11.
Bilayer Molecular Assembly at a Solid/Liquid Interface as Triggered by a Mild Electric Field 下载免费PDF全文
Qing‐Na Zheng Xuan‐He Liu Xing‐Rui Liu Ting Chen Hui‐Juan Yan Yu‐Wu Zhong Prof. Dr. Dong Wang Prof. Dr. Li‐Jun Wan 《Angewandte Chemie (International ed. in English)》2014,53(49):13395-13399
The construction of a spatially defined assembly of molecular building blocks, especially in the vertical direction, presents a great challenge for surface molecular engineering. Herein, we demonstrate that an electric field applied between an STM tip and a substrate triggered the formation of a bilayer structure at the solid–liquid interface. In contrast to the typical high electric‐field strength (109 V m?1) used to induce structural transitions in supramolecular assemblies, a mild electric field (105 V m?1) triggered the formation of a bilayer structure of a polar molecule on top of a nanoporous network of trimesic acid on graphite. The bilayer structure was transformed into a monolayer kagome structure by changing the polarity of the electric field. This tailored formation and large‐scale phase transformation of a molecular assembly in the perpendicular dimension by a mild electric field opens perspectives for the manipulation of surface molecular nanoarchitectures. 相似文献
12.
Kazukuni Tahara Dr. Koji Inukai Noritaka Hara Charles A. Johnson II Dr. Michael M. Haley Prof. Dr. Yoshito Tobe Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(28):8319-8328
Self‐assembled monolayers of a series of tetraalkoxy‐substituted octadehydrodibenzo[12]annulene (DBA) derivatives 1 c – g possessing butadiyne linkages were studied at the 1,2,4‐trichlorobenzene (TCB) or 1‐phenyloctane/graphite interface by scanning tunneling microscopy (STM). The purpose of this research is not only to investigate the structural variation of two‐dimensional (2D) monolayers, but also to assess a possibility for peri‐benzopolyacene formation by two‐dimensionally controlled polymerization on a surface. As a result, the formation of three structures, porous, linear, and lamella structures, were observed by changing the alkyl chain length and the solute concentration. The formation of multilayers of the lamella structure was often observed for all compounds. The selection of molecular networks is basically ascribed to intermolecular and molecule–substrate interactions per unit area and network density. The selective appearance of the linear structure of 1 d is attributed to favorable epitaxial registry matching between the substrate lattice and the overlayer lattice. Even though the closest interatomic distance between the diacetylenic units of the DBAs in the lamella structure (≈0.6 nm) is slightly larger compared to the typical distances necessary for topochemical polymerization, the reactivity toward external stimuli (electronic‐pulse irradiation from an STM tip and UV irradiation) was investigated. Unfortunately, no evidence for polymerization of the DBAs on the surface was observed. The present results indicate the necessity for further designing a suitable system for the on‐surface construction of structurally novel conjugated polymers, which are otherwise difficult to prepare. 相似文献
13.
Luc Piot Dr. Robert M. Meudtner Dipl.‐Chem. Tamer El Malah M. Sc. Stefan Hecht Prof. Dr. Paolo Samorì Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(19):4788-4792
Dynamic surfaces : The conformational transition of 2,6‐bis(1‐aryl‐1,2,3‐triazol‐4‐yl)pyridine (BTP) derivatives, triggered by a change in pH, has been observed with a sub‐nm resolution by STM at the solid–liquid interface. Upon addition of trifluoroacetic acid two different BTP molecules, each forming a highly ordered physisorbed monolayer, underwent significant conformational changes from their “rosette” to their “tetragon” forms, as reflected in dramatically altered 2D self‐assembly over large areas extending over hundreds of nanometers (see graphic).
14.
Remote Chiral Communication in Coadsorber‐Induced Enantioselective 2D Supramolecular Assembly at a Liquid/Solid Interface 下载免费PDF全文
Dr. Ting Chen Shu‐Ying Li Prof. Dong Wang Prof. Man Yao Prof. Li‐Jun Wan 《Angewandte Chemie (International ed. in English)》2015,54(14):4309-4314
Remote chiral communication in 2D supramolecular assembly at a liquid/solid interface was investigated at the molecular level. The stereochemical information in a chiral coadsorber was transmitted over a flexible spacer with a length of up to five methylene groups to a 2D supramolecular assembly of achiral building blocks with the cooperation of specific hydrogen bonding between the chiral coadsorber and achiral building blocks and the confinement effect during 2D crystallization. When the position of the stereogenic center was changed with respect to the stereocontrolling moiety, an odd–even effect was found. A stereogenic center closer to the stereocontrolling moiety transmitted the stereochemical information to the 2D supramolecular assembly more reliably. This result is beneficial not only for mechanistic understanding of chiral communication in 2D supramolecular assembly on surfaces but also for the rational design of homochiral supramolecular assemblies on surfaces. 相似文献
15.
Olivier Guillermet Dr. Eeva Niemi Dr. Samuthira Nagarajan Dr. Xavier Bouju Dr. David Martrou Dr. André Gourdon Dr. Sébastien Gauthier Dr. 《Angewandte Chemie (International ed. in English)》2009,48(11):1970-1973
Buckybowls : The adsorption of penta‐tert‐butylcorannulene, a molecule with fivefold symmetry, on Cu(111), a surface with threefold symmetry, is investigated by scanning tunneling microscopy complemented by structure calculations. The symmetry mismatch is resolved by the formation of threefold‐symmetric subunits consisting of three molecules, which combine with single molecules to form a nearly perfect filling of the plane (see picture).
16.
Daan Wouters Dr. Stephanie Hoeppener Dr. Ulrich S. Schubert Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(10):1732-1739
Surfaces with purposes : The electroinitiated patterning of self‐assembled monolayers enables the fabrication of a variety of complex nanostructures (see picture). The possibilities offered by the introduction of chemical selectivity through the local generation of chemically active groups and subsequent derivatization are reviewed, with a focus on progress in this area of research over the last four years.
17.
The concentration effect on a two‐dimensional (2D) self‐assembly of 4, 4′‐dihexadecyloxy‐benzophenon (DHB) has been investigated by scanning tunneling microscopy. The self‐assembly of DHB at the phenyloctane/graphite interface was concentration dependent. Under low concentration, the DHB molecules were adsorbed intactly on the graphite surface. With the increasing of concentration, one of side chains connecting the conjugated moiety stretched into the liquid phase. The coexistence of two self‐assembled structures was observed in a moderate concentration. The result indicated that the van der Waals interactions between the molecules and the graphite lattice were decreasing with the increasing concentration. After the samples were placed in ambient conditions over 24 h, a different self‐assembled structure was obtained on the gas/solid interface, in which the DHB molecules were adsorbed on the surface with only one of the side chains. Both the benzophenon core and the other side chain were extended to the gas phase. The results demonstrated that concentration played an important role in forming the 2D molecular self‐assembly and provided an efficient approach for the control of the DHB molecular nanostructure. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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19.
Aimei Gao Dr. Xinrui Miao Dr. Jie Liu Dr. Ping Zhao Dr. Jinwang Huang Dr. Wenli Deng Prof. Dr. 《Chemphyschem》2010,11(9):1951-1955
The synthesis and self‐assembly behavior of porphyrin–polypyridyl ruthenium(II) hybrid, which consists of a flexible alkyl chain attached with two conjugated moieties is described. The electronic absorption spectrum and emission spectra show that the [C8‐TPP‐(ip)Ru(phen)2](ClO4)2, abbreviated as (C8ip)TPPC has optical properties. Scanning tunneling microscopy (STM) studies found that the π–π interaction and metal–ligand interaction allow (C8ip)TPPC to form self‐assembled structure and have an edge‐on orientation on the highly oriented pyrolytic graphite (HOPG) surface. The multidentate structure in (C8ip)TPPC molecules act as linkers between the molecules and form metal–ligand coordination, which forces the assembly process in the direction of stable columnar arrays. In addition, although the sample was stored for two months in ambient conditions, STM experiments showed that the order of (C8ip)TPPC self‐assembly only slightly decreased which indicates that the self‐assembled monolayer is stable. This work demonstrates that introducing a metal‐ligand in the porphyrin‐polypyridyl compound is a useful strategy to obtain novel surface assemblies. 相似文献
20.
A triblock copolymer containing the complementary hydrogen bonding recognition pair ureidoguanosine–diaminonaphthyridine (UG–DAN) as pendant functional groups is synthesized using ring‐opening metathesis polymerization (ROMP). The norbornene‐based DAN monomer is shown to allow for a controlled polymerization when polymerized in the presence of a modified‐UG molecule that serves as a protecting group, subsequently allowing for the fabrication of functionalized triblock copolymers. The self‐assembly of the copolymers was characterized using dynamic light scattering and 1H NMR spectroscopy. It is demonstrated that the polymers self‐assemble via complementary hydrogen bonding motifs even at low dilutions, indicating intramolecular interactions.