Surface Adatom Mediated Structural Transformation in Bromoarene Monolayers: Precursor Phases in Surface Ullmann Reaction.

Structural transformations of supramolecular systems triggered by external stimuli maintain great potential for application in the fabrication of molecular storage devices. Using combined ultrahigh vacuum scanning tunneling microscopy, X-ray photoemission spectroscopy, and density functional theory calculations, we observed the surface adatom mediated structural transformation from 4,4''-dibromo- m-terphenyl (DMTP)-based halogen-bonded networks to DMTP-Cu(Ag) coordination networks on Cu(111) and Ag(111) at low temperatures. The halogen-bonded networks, which were formed on Cu(111) at 97 K and on Ag(111) at 93 K, consist of intact DMTP molecules stabilized by triple Br···Br bonds. The DMTP-Cu(Ag) coordination networks form on Cu(111) at 113 K and on Ag(111) at 103 K. They contain alternatingly arranged intact DMTP molecules and Cu(Ag) adatoms stabilized by weak C-Br···Cu(Ag) coordination bonds. Annealing the DMTP-Ag structure to 333 K leads to the initiation of C-Br bond scission. This observation suggests that the DMTP-Ag coordination network represents the intermediate phase ready for dehalogenation, which is the first step of the surface Ullmann reaction.

On-Surface Pseudo-High-Dilution Synthesis of Macrocycles: Principle and Mechanism.

Macrocycles have attracted much attention due to their specific "endless" topology, which results in extraordinary properties compared to related linear (open-chain) molecules. However, challenges still remain in their controlled synthesis with well-defined constitution and geometry. Here, we report the successful application of the (pseudo-)high-dilution method to the conditions of on-surface synthesis in ultrahigh vacuum. This approach leads to high yields (up to 84%) of cyclic hyperbenzene ([18]-honeycombene) via an Ullmann-type reaction from 4,4″-dibromo-meta-terphenyl (DMTP) as precursor on a Ag(111) surface. The mechanism of macrocycle formation was explored in detail using scanning tunneling microscopy and X-ray photoemission spectroscopy. We propose that the dominant pathway for hyperbenzene (MTP)6 formation is the stepwise desilverization of an organometallic (MTP-Ag)6 macrocycle, which forms via cyclization of (MTP-Ag)6 chains under pseudo-high-dilution conditions. The high probability of cyclization on the stage of the organometallic phase results from the reversibility of the C-Ag bond. The case is different from that in solution, in which cyclization typically occurs on the stage of a covalently bonded open-chain precursor. This difference in the cyclization mechanism on a surface compared to that in solution stems mainly from the 2D confinement exerted by the surface template, which hinders the flipping of chain segments necessary for cyclization.

On-Surface Synthesis and Characterization of Honeycombene Oligophenylene Macrocycles.

We report the on-surface formation and characterization of [30]-honeycombene, a cyclotriacontaphenylene, which consists of 30 phenyl rings (C180H120) and has a diameter of 4.0 nm. This shape-persistent, conjugated, and unsubstituted hexagonal hydrocarbon macrocycle was obtained by solvent-free synthesis on a silver (111) single-crystal surface, making solubility-enhancing alkyl side groups unnecessary. Side products include strained macrocycles with square, pentagonal, and heptagonal shape. The molecules were characterized by scanning tunneling microscopy and density functional theory (DFT) calculations. On the Ag(111) surface, the macrocycles act as molecular quantum corrals and lead to the confinement of surface-state electrons inside the central cavity. The energy of the confined surface state correlates with the size of the macrocycle and is well described by a particle-in-the-box model. Tunneling spectroscopy suggests conjugation within the planar rings and reveals influences of self-assembly on the electronic structure. While the adsorbed molecules appear to be approximately planar, the free molecules have nonplanar conformation, according to DFT.

The role of the substrate structure in the on-surface synthesis of organometallic and covalent oligophenylene chains.

The influences of the substrate structure on the formation of one-dimensional organometallic and covalent oligomers on a Cu(110) surface were studied using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS), and low energy electron diffraction (LEED) in ultrahigh vacuum (UHV). Vapor deposition of submonolayer 4,4''-dibromo-meta-terphenyl (DMTP) onto a Cu(110) surface at 300 K leads to scission of C-Br bonds and the formation of organometallic chains (cis/trans and all-trans) connected by C-Cu-C bonds. Larger islands (120 × 120 nm(2)) of all-trans zigzag organometallic chains as sole products were obtained by the deposition of DMTP onto Cu(110) held at 383 K. The domains are oriented along two directions with an angle of ±13° relative to the [0 0 1] direction due to the two-fold symmetry of the Cu(110) surface lattice. This study reveals at a sub-molecular level that the organometallic chains firstly lose copper atoms and then undergo C-C coupling into oligophenylene chains at a substrate temperature around 417 K. Annealing the large islands of organometallic chains at 458 K results in the formation of completely C-C covalently bonded zigzag oligophenylene chains. The zigzag angle of 125° slightly deviates from the ideal value of 120°. This is attributed to a stretching of the zigzag oligophenylene chains due to substrate template effects.

Confined Synthesis of Organometallic Chains and Macrocycles by Cu-O Surface Templating.

The bottom-up construction of low-dimensional macromolecular nanostructures directly on a surface is a promising approach for future application in molecular electronics and integrated circuit production. However, challenges still remain in controlling the formation of these nanostructures with predetermined patterns (such as linear or cyclic) or dimensions (such as the length of one-dimensional (1D) chains). Here, we demonstrate that a high degree of structural control can be achieved by employing a Cu(110)-(2×1)O nanotemplate for the confined synthesis of organometallic chains and macrocycles. This template contains ordered arrays of alternating stripes of Cu-O chains and bare Cu, the widths of which are controllable. Using scanning tunneling microscopy and low-energy electron diffraction, we show that well-defined, ordered 1D zigzag organometallic oligomeric chains with uniform lengths can be fabricated on the Cu stripes (width >5.6 nm) of the Cu(110)-(2×1)O surface. In addition, the lengths of the meta-terphenyl (MTP)-based chains can be adjusted by controlling the widths of the Cu stripes within a certain range. When reducing the widths of Cu stripes to a range of 2.6 to 5.6 nm, organometallic macrocycles including tetramer (MTP-Cu)4, hexamer (MTP-Cu)6, and octamer (MTP-Cu)8 species are formed due to the spatial confinement effect and attraction to the Cu-O chains. An overview of all formed organometallic macrocycles on the Cu stripes with different widths reveals that the origin of the formation of these macrocycles is the cis-configured organometallic dimer (MTP)2Cu3, which was observed on the extremely narrow Cu stripe with a width of 1.5 nm.

Assembling molecular Sierpinski triangle fractals.

Fractals, being "exactly the same at every scale or nearly the same at different scales" as defined by Benoit B. Mandelbrot, are complicated yet fascinating patterns that are important in aesthetics, mathematics, science and engineering. Extended molecular fractals formed by the self-assembly of small-molecule components have long been pursued but, to the best of our knowledge, not achieved. To tackle this challenge we designed and made two aromatic bromo compounds (4,4″-dibromo-1,1':3',1″-terphenyl and 4,4‴-dibromo-1,1':3',1″:4″,1‴-quaterphenyl) to serve as building blocks. The formation of synergistic halogen and hydrogen bonds between these molecules is the driving force to assemble successfully a whole series of defect-free molecular fractals, specifically Sierpinski triangles, on a Ag(111) surface below 80 K. Several critical points that govern the preparation of the molecular Sierpinski triangles were scrutinized experimentally and revealed explicitly. This new strategy may be applied to prepare and explore various planar molecular fractals at surfaces.

Surface-assisted formation, assembly, and dynamics of planar organometallic macrocycles and zigzag shaped polymer chains with C-Cu-C bonds.

The formation, structure, and dynamics of planar organometallic macrocycles (meta-terphenyl-Cu)n and zigzag-shaped one-dimensional organometallic polymers on a Cu(111) surface were studied with scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Vapor deposition of 4,4″-dibromo-meta-terphenyl (DMTP) onto Cu(111) at 300 K leads to C-Br bond scission and formation of C-Cu-C bonds, which connect neighboring meta-terphenyl fragments such that room-temperature stable macrocycles and zigzag chains are formed. The chains self-assemble to form islands, which are elongated in the direction of the chains. If DMTP is deposited onto Cu(111) held at 440 K, the island size is drastically increased (>200 × 200 nm(2)). STM sequences show the formation of ordered structures through reversible scission and reformation of the C-Cu-C bonds. The cyclic organometallic species such as the hexamer (meta-terphenyl-Cu)6 may represent intermediates in the surface-confined Ullmann synthesis of hydrocarbon macrocycles such as the recently discovered hyperbenzene.

Cobalt catalysis in the gas phase: experimental characterization of cobalt(I) complexes as intermediates in regioselective Diels-Alder reactions.

In situ-formed cobalt(I) complexes are proposed to act as efficient catalysts in regioselective Diels-Alder reactions of unactivated substrates such as 1,3-dienes and alkynes. We report the first experimental evidence for the in situ reduction of CoBr2(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane] by Zn/ZnI2 to [Co(I)(dppe)](+) by means of electrospray MS(n) experiments. Additionally, the reactivities of Co(II) and Co(I) dppe complexes toward the Diels-Alder substrates isoprene and phenylacetylene were probed in gas-phase ion/molecule reactions (IMRs). Isoprene and phenylacetylene were introduced into the mass spectrometer via the buffer gas flow of a linear ion trap. The IMR experiments revealed a significantly higher substrate affinity of [Co(I)(dppe)](+) compared with [Co(II)Br(dppe)](+). Furthermore, the central intermediate of the solution-phase cobalt-catalyzed Diels-Alder reaction, [Co(I)(dppe)(isoprene)(phenylacetylene)](+), could be generated via IMR and examined in the gas phase. Collision activation of this complex ion delivered evidence for the gas-phase reaction of isoprene with phenylacetylene in the coordination sphere of the cobalt ion. The experimental findings are consistent with the results of quantum-chemical calculations on all of the observed Co(I) dppe complex ions. The results constitute strong analytical evidence for the formation and importance of different cobalt(I) species in regioselective Diels-Alder reactions of unactivated substrates and identify [Co(I)(dppe)](+) as the active Diels-Alder catalyst.

Surface-assisted organic synthesis of hyperbenzene nanotroughs.

A hexagonal macrocycle consisting of 18 phenylene units (hyperbenzene) was synthesized on a Cu(111) surface in ultrahigh vacuum by Ullmann coupling of six 4,4''-dibromo-m-terphenyl molecules. The large diameter of 21.3 Šand the ability to assemble in arrays makes hyperbenzene an interesting candidate for a nanotrough that could enclose metallic, semiconducting, or molecular quantum dots.

Multidirectional cobalt-catalyzed Diels-Alder/1,4-hydrovinylation sequences.

The combination of two powerful cobalt-catalyzed carbon-carbon bond forming transformations, namely, the Diels-Alder and the 1,4-hydrovinylation reaction, in a tandem or a sequential one-pot procedure, opened up a concise and efficient route to polysubstituted aromatic systems and cyclohex-3-enone derivatives. Furthermore, ozonolysis of the latter products led to polycarbonyl compounds with tailored carbonyl group distances which could be characterized via their respective BF(2)-borinane complexes. The cobalt catalysts tolerated several functional groups, and a flexible approach to polyfunctionalized compounds in concise fashion was described.