Apical Functionalization of Tribenzotriquinacenes

Dhara, Ayan; Weinmann, Joshua; Krause, Ana‐Maria; Beuerle, Florian

doi:10.1002/chem.201602622

Cited by 12 publications

(10 citation statements)

References 54 publications

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“…Beuerle and co-workers have recently reported on the efficient and flexible functionalization of the apex position of TBTQ. 29 Also for Me-TBTQ, the lattice parameters a and b of the two-dimensional hexagonal lattice on Ag(111) differ largely from the values in a bulk single crystal of 2. Whereas a = b = 14.96 Å have been measured by single-crystal X-ray crystallography, 27 a and b have a value of 18.0 ± 1.1 Å when 2 is deposited on Ag(111).…”

Section: ■ Results and Discussionmentioning

confidence: 97%

“…described a higher-yielding alternative strategy for the synthesis of TBTQ 1 , which features triple cyclization as the key step . According to X-ray single-crystal structure analyses, both TBTQ molecules shown here adopt a perfect C 3 v conformation in the solid state, where the three indane wings adopt mutually orthogonal orientations. , The rigid conformation and orthogonal geometry of the TBTQ motif have already been utilized as a building block for supramolecular assemblies such as organic cages, − host–guest complexes, − and chemosensors . Functionalization of TBTQs at different positions can also improve the solubility and pave the way to an extended carbon network.…”

Section: Introductionmentioning

confidence: 91%

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Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

et al. 2019

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The structure of two-dimensional layers of organic compounds on metal surfaces is of great interest for the fabrication of devices in the field of organic electronics. To progress in this area, a deeper understanding of intermolecular interactions and charge transfer processes between organic molecules and a metal substrate is required. Here, the two-dimensional self-assembly of tribenzotriquinacenes (TBTQs) on Ag(111) was studied by scanning tunneling microscopy under ultrahigh vacuum conditions. Highly ordered monolayers of tribenzotriquinacene (TBTQ) and centro-methyl tribenzotriquinacene (Me-TBTQ) were observed for the first time. At low to moderate coverage, both of these bowl-shaped molecules adsorb with the bowl opening faced downward, appearing in two orientations that are rotated by 14° from the high-symmetry axis of the Ag(111) surface. At high TBTQ coverage, extended islands with a self-assembled highly ordered windmill nanostructure dominate the surface, interspaced with nanometer-sized openings. This windmill structure is absent in Me-TBTQ, which immediately forms double-layered regions at high coverage. Scanning tunneling spectroscopy measurements, which probe the local density of states, identify a shift of the Ag(111) surface state in the presence of the TBTQ molecules. Investigations such as these into the self-assembly of curved aromatics provide a foundation for further work on the construction of multilayer nanostructures and the production of electronic devices.

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Section: ■ Results and Discussionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 91%

Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

et al. 2019

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“…Further functionalization of TBTQs is possible through reaction at the phenylene units or at the benzhydrylic positions . Recently, the first apical functionalization of TBTQ at the central methine carbon atom was developed, thus opening another route in TBTQ chemistry …”

Section: Methodsmentioning

confidence: 99%

Switching the Statistical C₃/C₁ Ratio in the Threefold Aromatic Substitution of Tribenzotriquinacenes towards the C₃ Isomer

2018

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Tribenzotriquinacene (TBTQ) is ab owl-shaped molecule that has been widely used as am olecular building blocki ns upramolecular and materials chemistry.E specially C 3 -symmetric threefold-substituted TBTQs are interesting for these purposes.U ntil nowageneral and selective synthetic approach to those C 3 -symmetric products was lacking, mainly because the typically used electrophilic aromatic substitution reactions of the parent TBTQ hydrocarbons produce predominantly the C 1 isomer over the C 3 isomer (3:1 statistical ratio). Herein we introduce athreefold borylation of TBTQ with the C 3 isomer as the main product (2.6:1 C 3 /C 1 ratio). The borylated TBTQ can be converted in good yields into other C 3 -symmetric TBTQs,thus allowing straightforwards ynthetic access to new building blocks for supramolecular and materials chemistry.

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“…Therefore, the use of iodonium salts for the alkynylation of enolates failed to be broadly adopted by the organic chemistry community. One of the rare recent reports by Beuerle and coworkers describes the use of TMS-protected ethynyl iodonium salt 17 to install a terminal acetylene onto dione 16 (Scheme 4) 47 . The resulting product 18 was then used in the synthesis of apically functionalized tribenzotriquinacenes (TBTQ) 19, multi-functional molecules of interest in the field of supramolecular chemistry.…”

Section: Alkynylation Reactionsmentioning

confidence: 99%

Alkynylations and Vinylations

Hari

Nicolai

Waser

2018

Patai's Chemistry of Functional Groups

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Alkynes and alkenes are important building blocks in synthetic organic chemistry and related domains. Therefore, unceasing efforts have been invested to develop new methods to introduce these valuable functional groups. Traditionally, most alkynylation and alkenylation reactions have relied on the use of olefins and acetylenes as nucleophilic reacting species, limiting the accessible structural diversity. The discovery of the unique properties of hypervalent iodine has more recently significantly broadened the scope of electrophilic ethynylation and vinylation reactions. Alkynyl and alkenyl iodonium salts were first recognized as powerful reagents to install electrophilic acetylenes and olefins onto nucleophilic substrates under mild conditions. Their low stability has however narrowed the area of their applications. Since 2009, more stable cyclic benziodoxol(on)e reagents have shown their superiority as effective electrophilic alkynylating and alkenylating reagents in numerous metal-free and metal-catalyzed olefination and ethynylation reactions of carbon centered nucleophiles, radicals, and heteroatom nucleophiles. In this chapter, an overview of the progress in the field is presented, including a short summary of pioneering works, followed by a more in-depth description of recent results.

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Apical Functionalization of Tribenzotriquinacenes

Cited by 12 publications

References 54 publications

Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

Switching the Statistical C₃/C₁ Ratio in the Threefold Aromatic Substitution of Tribenzotriquinacenes towards the C₃ Isomer

Alkynylations and Vinylations

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Apical Functionalization of Tribenzotriquinacenes

Cited by 12 publications

References 54 publications

Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

Switching the Statistical C3/C1 Ratio in the Threefold Aromatic Substitution of Tribenzotriquinacenes towards the C3 Isomer

Alkynylations and Vinylations

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Product

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About

Switching the Statistical C₃/C₁ Ratio in the Threefold Aromatic Substitution of Tribenzotriquinacenes towards the C₃ Isomer