391198-48-4

Upstream product

• 89343-06-6 tris-iso-propylsilyl acetylene 
• 106-40-1 4-bromo-aniline 
• 106-47-8 4-chloro-aniline 
• 540-37-4 p-aminoiodobenzene 

Downstream Products

• 901764-96-3 N,N-bis(4-tert-butylphenyl)-4-(triisopropylsilylethynyl)aniline 
• 901764-97-4 N,N-bis(4-decyloxyphenyl)-4-(triisopropylsilylethynyl)aniline 

Relevant academic research and scientific papers

A fluorescent, shape-persistent dendritic host with photoswitchable guest encapsulation and intramolecular energy transfer

A fluorescent and photoresponsive host based on rigid polyphenylene dendrimers (PPDs) has been synthesized. The key building block for the divergent dendrimer buildup is a complex tetracyclone 12 containing azobenzenyl, pyridyl, and ethynyl entities. The

Efficient access to materials-oriented aromatic alkynes: Via the mechanochemical Sonogashira coupling of solid aryl halides with large polycyclic conjugated systems

Sonogashira coupling represents an indispensable tool for the preparation of organic materials that contain C(sp)-C(sp2) bonds. Improving the efficiency and generality of this methodology has long been an important research subject in materials science. Here, we show that a high-temperature ball-milling technique enables the highly efficient palladium-catalyzed Sonogashira coupling of solid aryl halides that bear large polyaromatic structures including sparingly soluble substrates and unactivated aryl chlorides. In fact, this new protocol provides various materials-oriented polyaromatic alkynes in excellent yield within short reaction times in the absence of bulk reaction solvents. Notably, we synthesized a new luminescent material via the mechanochemical Sonogashira coupling of poorly soluble Vat Red 1 in a much higher yield compared to those obtained using solution-based conditions. The utility of this method was further demonstrated by the rapid synthesis of a fluorescent metal-organic framework (MOF) precursor via two sequential mechanochemical Sonogashira cross-coupling reactions. The present study illustrates the great potential of Sonogashira coupling using ball milling for the preparation of materials-oriented alkynes and for the discovery of novel functional materials.

Development of helical aromatic amide foldamers with a diphenylacetylene backbone

We designed and synthesized aromatic polyamides with a diphenylacetylene backbone, α-DPA and β-DPA, bearing (S)-α-and (S)-β-methyl-substituted triethyleneglycol (TEG) side chains, respectively, and examined their conformations in solution. Both polymers exhibit strong, solvent polarity-dependent circular dichroism spectra, which indicated that they take helical conformations in low-polarity solvents. The spectra were mirror images, depending on the chiral position of the side chains. Thus, the polyamide α-DPA bearing (S)-α-methyl-substituted TEG groups takes a left-handed helical conformation, while the polyamide β-DPA with (S)-β-methyl-substituted TEG groups takes a right-handed helical conformation. The difference in the screw sense of α-DPA and β-DPA would be caused by the steric interaction between the main chain and the side chain, as observed in poly(p-benzamide) possessing (S)-β-methyl-substituted TEG side chains (β-PA) because the large cavity of the helical structure of DPA would disturb the solvophobically induced helical folding. Detailed conformational analyses of the oligoamides 6-12 with β-methyl-substituted TEG groups were conducted. Theoretical calculations indicated that the oligoamides with β-methyl-substituted TEG groups exist in a helical conformation with a cavity of 7 ? in diameter. The 1H NMR spectra of the oligomers revealed interactions with small anions such as chloride and acetate anions and with pyridinium cations.

Borazino-Doped Polyphenylenes

The divergent synthesis of two series of borazino-doped polyphenylenes, in which one or more aryl units are replaced by borazine rings, is reported for the first time, taking advantage of the decarbonylative [4 + 2] Diels-Alder cycloaddition reaction between ethynyl and tetraphenylcyclopentadienone derivatives. Because of the possibility of functionalizing the borazine core with different groups on the aryl substituents at the N and B atoms of the borazino core, we have prepared borazino-doped polyphenylenes featuring different doping dosages and orientations. To achieve this, two molecular modules were prepared: a core and a branching unit. Depending on the chemical natures of the central aromatic module and the reactive group, each covalent combination of the modules yields one exclusive doping pattern. By means of this approach, three- and hexa-branched hybrid polyphenylenes featuring controlled orientations and dosages of the doping B3N3 rings have been prepared. Detailed photophysical investigations showed that as the doping dosage is increased, the strong luminescent signal is progressively reduced. This suggests that the presence of the B3N3 rings engages additional deactivation pathways, possibly involving excited states with an increasing charge-separated character that are restricted in the full-carbon analogues. Notably, a strong effect of the orientational doping on the fluorescence quantum yield was observed for those hybrid polyphenylene structures featuring low doping dosages. Finally, we showed that Cu-catalyzed 1,3-dipolar cycloaddition is also chemically compatible with the BN core, further endorsing the inorganic benzene as a versatile aromatic scaffold for engineering of molecular materials with tailored and exploitable optoelectronic properties.

Nanostructured monolayers on carbon substrates prepared by electrografting of protected aryldiazonium salts

The electrogeneration of aryl radicals from protected diazonium salts combined with protection-deprotection steps was evaluated to design functional monolayers on carbon substrates with a well-controlled organization at the nanometric scale. The structure

Synthesis and optical properties of molecular rods comprising a central core-substituted naphthalenediimide chromophore for carbon nanotube junctions

The synthesis of a series of molecular rods 1-5, designed to bridge the gap of a carbon nanotube junction in order to emit light as a characteristic signal of integrated molecules, is reported. The molecular rods consist of a central naphthalenediimide (NDI) core, which itself is substituted with benzylamino and benzylsulfanyl groups, providing distinct absorption and emission properties. The NDI core is embedded in an oligo(phenylene ethynylene) (OPE) system providing the rod-like structure required to bridge gaps between nanoelectrodes. The number of repeating units of the OPE is varied to adjust the length of the target compounds between 2.3 and 6.6 nm. The OPE parts are terminally functionalized with polyaromatic hydrocarbon groups (naphthalene, phenanthrene, anthracene or pyrene), which possess affinity with the surface of the carbon nanotubes due to van der Waals interactions. Synthetic protocols based on Sonogashira-Hagihara couplings were developed to build up the OPE backbone. Bifunctional iodophenyl acetylene derivative 33 served as a key building block in a coupling-deprotecting-coupling sequence. The NDI building block was synthesized by an aromatic nucleophilic substitution reaction of 2,6-dichloro-1,4,5,8-tetracarboxylic acid naphthalenediimide derivative 9 and the corresponding amine and sulfide (i.e., 11, 12), respectively. The convergent synthesis allows modular assembly of the NDI and OPE parts in a final Sonogashira-Hagihara coupling reaction. The target structures were fully characterized by NMR spectroscopy and mass spectrometry. Further, the optical properties of compounds 3-5 in solution, and on a graphene surface were qualitatively investigated. A Dexter-type energy transfer from the OPE unit to the NDI unit was observed. The studies of target structures 3-5 revealed that diamino-functionalized compound 3 is ideally suited for the envisaged single molecule electroluminescence experiments. The synthesis of a series of over 6-nm long modular rods with a central decoupled naphthalenediimide (NDI) chromophore isreported. Their spectroscopic properties are adjusted by varying the substituents of the NDI core

Phenylene ethynylene pentamers for organic electroluminescence

An isomeric family of eighteen triisopropylsilyl-capped phenylene ethynylene pentamers (molecular formula C60H62Si2) has been prepared by using fast parallel synthesis, for organic electroluminescence. Each pentamer was grown on a polymer support of propylaminomethylated polystyrene by using a series of palladium-catalysed reactions between aryl iodides and alkynes. "Tea bag" technology was used to carry out several different reactions simultaneously in the same flask. Here I present the syntheses of the materials, compare their photoluminescence both in solution and in the solid state (amorphous thin films) and describe the incorporation of the most promising pentamer into organic electroluminescence devices.