Angew Chem Int Ed Engl
September 2024
We show an unexpected aggregation phenomenon of a long oligoyne (Py[16]) with 16 contiguous triple bonds and endcapped with bulky 3,5-bi(3,5-bis-tert-butylphenyl)pyridine groups. Aggregation of 1D π-conjugated oligoyne chains is rare given the minimal π-π intermolecular interactions as well as its flexibility that works against self-assembly. In dilute solutions, the reversible aggregation of Py[16] initiates at low temperature in the range of 140-180 K, and is not observed for shorter oligoynes in this series.
View Article and Find Full Text PDFMolecular rings of carbon atoms (cyclo[]carbons, or C) are excellent benchmarking systems for testing quantum chemical theoretical methods and valuable precursors to other carbon-rich materials. Odd- cyclocarbons, which have been elusive to date, are predicted to be even less stable than even- cyclocarbons. We report the on-surface synthesis of cyclo[13]carbon, C, by manipulation of decachlorofluorene with a scanning probe microscope tip.
View Article and Find Full Text PDFPolyynes are chains of sp carbon atoms with alternating single and triple bonds. As they become longer, they evolve towards carbyne, the 1D allotrope of carbon, and they become increasingly unstable. It has been anticipated that long polyynes could be stabilized by supramolecular encapsulation, by threading them through macrocycles to form polyrotaxanes-but, until now, polyyne polyrotaxanes with many threaded macrocycles have been synthetically inaccessible.
View Article and Find Full Text PDFSynthetic carbon allotropes such as graphene, carbon nanotubes and fullerenes have revolutionized materials science and led to new technologies. Many hypothetical carbon allotropes have been discussed, but few have been studied experimentally. Recently, unconventional synthetic strategies such as dynamic covalent chemistry and on-surface synthesis have been used to create new forms of carbon, including γ-graphyne, fullerene polymers, biphenylene networks and cyclocarbons.
View Article and Find Full Text PDFThe formation and study of molecules that model the sp-hybridized carbon allotrope, carbyne, is a challenging field of synthetic physical organic chemistry. The target molecules, oligo- and polyynes, are often the preferred candidates as models for carbyne because they can be formed with monodisperse lengths as well as defined structures. Despite a simple linear structure, the synthesis of polyynes is often far from straightforward, due in large part to a highly conjugated framework that can render both precursors and products highly reactive, i.
View Article and Find Full Text PDFThe versatility of carbon is revealed in its all-carbon forms (allotropes), which feature unique properties (consider the differences between diamond, graphite, graphene and fullerenes). Beyond natural sources, there are many opportunities to expand the realm of carbon chemistry through the study of new carbon forms. In this work, the synthesis of oligo-/polyynes is used to model the elusive carbyne.
View Article and Find Full Text PDFThe hierarchical synthesis of three porphyrin and four bisporphyrin derivatives is presented. This strategy relies on the incorporation of linkers based on azo moieties appended with pyridyl and/or acetylenic groups that facilitate axial coordination to Ga- and Ru-metalloporphyrins. These porphyrinic systems allow for a quantitative analysis of the effects of diamagnetic anisotropy (DA) by using H NMR spectroscopic and X-ray crystallographic analyses.
View Article and Find Full Text PDFThe process of singlet fission (SF) produces two triplet excited states (T + T) from one singlet excited exciton (S) and a molecule in its ground state (S). It, thus, possesses the potential to boost the solar cell efficiency above the thermodynamic Shockley-Queisser limit of 33%. A key intermediate in the SF mechanism is the singlet correlated triplet pair state (TT).
View Article and Find Full Text PDFMultidimensional, conjugated building blocks have been formed through the axial coordination of polyynes to the central Ga atom of tetraarylporphyrins. Electron deficient pentafluorophenyl substituents in the meso-positions provide more stable σ-acetylide complexes to Ga than analogous structures with tert-butylphenyl groups. Mono-, di-, and triynes have been used, including a pyridyl endcapped diyne that allows for formation of porphyrin triads through coordination of the pyridyl ligand to a Ru porphyrin.
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