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The formation of azo compounds via redox cross-coupling of nitroarenes and arylamines, challenging in solution phase chemistry, is achieved by on-surface chemistry. Reaction products are analyzed with a cryogenic scanning tunneling microscope (STM) and X-ray photoelectron spectroscopy (XPS). By using well-designed precursors containing both an amino and a nitro functionality, azo polymers are prepared on surface via highly efficient nitro-amino cross-coupling. Experiments conducted on other substrates and surface orientations reveal that the metal surface has a significant effect on the reaction efficiency. The reaction was further found to proceed from partially oxidized/reduced precursors in dimerization reactions, shedding light on the mechanism that was studied by DFT calculations.
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Single chains of metal atoms are expected to be perfect one-dimensional nanowires in nanotechnology, due to their quantum nature including tunable electronic or spin coupling strengths. However, it is still rather difficult to fabricate such nanowires with metallic atoms under directional and separation control. Here, we succeeded in building higher-order single diamondoid-chains from the lower-order chains using a chemically well-controlled approach that employs diamondoids on metal surfaces. This approach results in higher-order diamondoid double chains by linking two neighboring single chains, and ultimately forms a central chain consisting of single Cu atoms suspended by the diamantane framework. The suspended Cu atoms are placed above the metal surface with a periodic distance of 0.67 ± 0.01 nm. Our bottom-up approach will allow detailed experimental investigations of the properties of these exciting suspended metal atoms (for example, quantized conductance, spin coupling, as well as transfer, etc.). Furthermore, we also identified different spatial configurations on the metal surfaces in on-surface reaction processes using high-resolution AFM imaging and density functional theory computations. Our findings broaden the on-surface synthesis concept from 2D planar aromatic molecules to 3D bulky aliphatic molecules.
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A series of Pt(II) complexes with tetradentate luminophores has been designed, synthesized, and deposited on coinage metal surfaces with the aim to produce highly planar self-assembled monolayers. Low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations reveal a significant initial nonplanarity for all complexes. A subsequent metal-catalyzed separation of the nonplanar moiety at the bridging unit via the scission of a C-N bond is observed, leaving behind a largely planar core complex. The activation barrier of this bond scission process is found to depend strongly on the chemical nature of both bridging group and coordination plane, and to increase from Cu(111) through Ag(111) to Au(111).
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Polymerization of a biphenyl bis α-diazo ketone on Cu(111) and Au(111) surfaces to provide furandiyl bridged poly-para-phenylenes is reported. Polymerization on Cu(111) occurs via initial N2 fragmentation leading to Cu-biscarbene complexes at room temperature as polymeric organometallic structure. At 135 °C, carbene coupling affords polymeric α,ß-unsaturated 1,4-diketones, while analogous alkene formation on the Au(111) surface occurs at room temperature. Further temperature increase leads to deoxygenative cyclization of the 1,4-diketone moieties to provide alternating furandiyl biphenyl copolymers on Cu(111) (165 °C) and Au(111) (240 °C) surfaces. This work shows a new approach to generate Cu-biscarbene intermediates on surfaces, opening the pathway for the controlled generation of biphenyl copolymers.
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This work reports the influence of molecular coverage in on-surface C-C-bond formation on reaction outcome. 6-Ethynyl-2-naphthoic acid (ENA) was chosen as organic component and Ag(111) as substrate. The alkyne moiety in ENA can either react by dimerization to ENA dimers (Glaser coupling or hydroalkynylation) or cyclotrimerization to generate a benzene core as connecting moiety. Dimer formation is preferred at high surface coverage whereas trimerization is the major reaction pathway at low coverage. Mechanistic studies are provided.
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Silylation and desilylation are important functional group manipulations in solution-phase organic chemistry that are heavily used to protect/deprotect different functionalities. Herein, we disclose the first examples of the σ-bond metathesis of silylated alkynes with aromatic carboxylic acids on the Ag(111) and Au(111) surfaces to give the corresponding terminal alkynes and silyl esters, which is supported by density functional theory calculations and further confirmed by X-ray photoelectron spectroscopy analysis. Such a protecting group strategy applied to on-surface chemistry allows self-assembly structures to be generated from molecules that are inherently unstable in solution and in the solid state. This is shown by the successful formation of self-assembled hexaethynylbenzene at Ag(111). Furthermore, it is also shown that on the Au(111) surface this σ-bond metathesis can be combined with Glaser coupling to fabricate covalent polymers via a cascade process.
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Herein we report the on-surface oxidative homocoupling of 6,6'-(1,4-buta-1,3-diynyl)bis(2-naphthoic acid) (BDNA) via bisacylperoxide formation on different Au substrates. By using this unprecedented dehydrogenative polymerization of a biscarboxylic acid, linear poly-BDNA with a chain length of over 100â nm was prepared. It is shown that the monomer BDNA can be prepared inâ situ at the surface via on-surface Glaser coupling of 6-ethynyl-2-naphthoic acid (ENA). Under the Glaser coupling conditions, BDNA directly undergoes polymerization to give the polymeric peroxide (poly-BDNA) representing a first example of an on-surface domino reaction. It is shown that the reaction outcome varies as a function of surface topography (Au(111) or Au(100)) and also of the surface coverage, to give branched polymers, linear polymers, or 2D metal-organic networks.
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Aryl propiolic acids are introduced as a new class of monomers in the field of on-surface chemistry to build up poly(arylenebutadiynylenes) through decarboxylative Glaser coupling. As compared to aryl alkynes that are routinely used in the on-surface Glaser coupling, it is found that the decarboxylative coupling occurs at slightly lower temperature and with excellent selectivity. Activation occurs through decarboxylation for the propiolic acids, whereas the classical Glaser coupling is achieved through alkyne CH activation, and this process shows poor selectivity. The efficiency of the decarboxylative coupling is documented by the successful polymerization of bis(propiolic acids) as monomers. It is also found that the new activation mode is compatible with aryl bromide functionalities, which allows the formation of unsymmetric metal-organic polymers on the surface by chemoselective sequential reactions. All transformations are analyzed by a scanning tunneling microscope and are further studied by density functional theory calculations.
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Molecular spatial conformational evolution following the corresponding chemical reaction pathway at surfaces is important to understand and optimize chemical processes. Combining experimental and theoretical methods, the sequential N-H and C-H dehydrogenation of pyromellitic diimide (PMDI) on a Cu(111) surface are reported. STM experiments and atomistic modeling allow structural analysis at each well-defined reaction step. First, exclusively the aromatic N-H dehydrogenation of the imide group is observed. Subsequently, the C-H group at the benzene core of PMDI gets activated leading to a dehydrogenation reaction forming metalorganic species where Cu adatoms pronouncedly protruding from the surface are coordinated by one or two PMDI ligands at the surface. All reactions of PMDI induce conformational changes at the surface as confirmed by STM imaging and DFT simulations. Such conformational evolution in sequential N-H and C-H activation provides a detailed insight to understand molecular dehydrogenation processes at surfaces.
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Element-element double bonds of group 14 elements can be formed in solution, but generally only by applying harsh reductive conditions using sterically highly shielded tetryl halides as precursors. The two-dimensional confinement in surface-assisted polymerization represents a valuable alternative to access such reactive compounds, as it allows shielding of the labile entities without requiring bulky residues and catalytic activation of the reactive groups. Here, we demonstrate Si-Si bond formation in on-surface chemistry. Polymerization upon multiple Si-H bond dissociation and subsequent Si-Si bond formation was achieved on Au(111) and Cu(111) surfaces by using two different monomers, each containing two silicon functional groups (CH3SiH2 or SiH3) attached to an aromatic backbone, leading to polymeric disilenes that interact with the surface. A combination of experimental and theoretical studies corroborates the formation of covalent Si-Si bonds between the long, highly ordered polymer chains with high diastereoselectivity. The reactive Si=Si bonds formally generated via double dehydrogenative coupling are stabilized via covalent Si-surface interaction.
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The on-surface dimerization reaction of an organic nitrile on Au(111) is reported. The formation of the product, which contains five newly formed σ-bonds and a diazapyrene core structure, was investigated and characterized by scanning tunneling microscopy. Experimental and computational studies of reference compounds support our findings.
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Atomic force microscopy is an impressive tool with which to directly resolve the bonding structure of organic compounds1-5. The methodology usually involves chemical passivation of the probe-tip termination by attaching single molecules or atoms such as CO or Xe (refs 1,6-9). However, these probe particles are only weakly connected to the metallic apex, which results in considerable dynamic deflection. This probe particle deflection leads to pronounced image distortions, systematic overestimation of bond lengths, and in some cases even spurious bond-like contrast features, thus inhibiting reliable data interpretation8-12. Recently, an alternative approach to tip passivation has been used in which slightly indenting a tip into oxidized copper substrates and subsequent contrast analysis allows for the verification of an oxygen-terminated Cu tip13-15. Here we show that, due to the covalently bound configuration of the terminal oxygen atom, this copper oxide tip (CuOx tip) has a high structural stability, allowing not only a quantitative determination of individual bond lengths and access to bond order effects, but also reliable intermolecular bond characterization. In particular, by removing the previous limitations of flexible probe particles, we are able to provide conclusive experimental evidence for an unusual intermolecular N-Au-N three-centre bond. Furthermore, we demonstrate that CuOx tips allow the characterization of the strength and configuration of individual hydrogen bonds within a molecular assembly.
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Flexible sensors have attracted more and more attention as a fundamental part of anthropomorphic robot research, medical diagnosis and physical health monitoring. Here, we constructed an ultrasensitive and passive flexible sensor with the advantages of low cost, lightness and wearability, electric safety and reliability. The fundamental mechanism of the sensor is based on triboelectric effect inducing electrostatic charges on the surfaces between two different materials. Just like a plate capacitor, current will be generated while the distance or size of the parallel capacitors changes caused by the small mechanical disturbance upon it and therefore the output current/voltage will be produced. Typically, the passive sensor unambiguously monitors muscle motions including hand motion from stretch-clench-stretch, mouth motion from open-bite-open, blink and respiration. Moreover, this sensor records the details of the consecutive phases in a cardiac cycle of the apex cardiogram, and identify the peaks including percussion wave, tidal wave and diastolic wave of the radial pulse wave. To record subtle human physiological signals including radial pulsilogram and apex cardiogram with excellent signal/noise ratio, stability and reproducibility, the sensor shows great potential in the applications of medical diagnosis and daily health monitoring.
Assuntos
Actigrafia/instrumentação , Sistemas Microeletromecânicos/instrumentação , Monitorização Ambulatorial/instrumentação , Atividade Motora/fisiologia , Músculo Esquelético/fisiologia , Transdutores , Balistocardiografia , Vestuário , Desenho de Equipamento , Análise de Falha de Equipamento , Humanos , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
Reversible molecular switches with molecular orientation as the information carrier have been achieved on individual fullerene molecules adsorbed on Si (111) surface at room temperature. Scanning tunneling microscopy imaging directly demonstrates that the orientation of individual fullerene with an adsorption geometry of 5-6 bond is rotated by integral times as 30 degree after a pulse bias is applied between the STM tip and the molecule. Dependences of the molecular rotation probability on the voltage and the process of applied bias reveal that the rotation of a fullerene molecule takes place in two successive steps: the bonding between the fullerene and the Si surface is firstly weakened via electronic excitation and then low energy electron bombardment causes the molecule to rotate by certain degree.