A facile method to prepare one-dimensional (1D) organometallic nanomaterials from various ethynyl-substituted molecules is reported. The reactions of 3-chloro-1-ethynylbenzene, -Bu-phenylacetylene and 4-ethynylbiphenyl with Cu ions in acetonitrile yield nanorod-shaped copper acetylides (Cu-C≡C-R) crystals. In the case of linear alkynes, namely, propyne, 1-pentyne and 1-hexyne, it was found that using an aqueous ammonia/ethanol mixed solvent instead of acetonitrile is a better approach to obtain 1D nanostructures. This procedure also enables us to prepare functional 1D nanomaterials. We demonstrate the preparation of a paramagnetic nanorod from the organic radical -ethynylphenyl nitronyl nitroxide, and fluorescent nanorods from 9-ethynylphenanthrene and 2-ethynyl-9,9'-spirobifluorene.
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http://dx.doi.org/10.1002/open.201900145 | DOI Listing |
Molecules
January 2025
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Developing a new type of circularly polarized luminescent active small organic molecule that combines high fluorescence quantum yield and luminescence dissymmetric factor in both solution and solid state is highly challenging but promising. In this context, we designed and synthesized a unique triarylborane-based [2.2]paracyclophane derivative, , in which an electron-accepting [(2-dimesitylboryl)phenyl]ethynyl group and an electron-donating -diphenylamino group are introduced into two different benzene rings of [2.
View Article and Find Full Text PDFJ Org Chem
July 2024
Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
In contrast to self-assembly in solution systems, the construction of well-defined assemblies in the solid state has long been identified as a challenging task. Herein, we report the formation of tweezers-shaped molecules into various assemblies through a solid-state self-assembly strategy. The relatively flexible molecular tweezers undergo exclusive and quantitative assembly into either cyclic hexamers or a porous network through classical recrystallization or the exposure of powders to solvent vapor, despite the fact that they form only dimers in solution.
View Article and Find Full Text PDFChemistry
February 2024
Department of Chemistry, National Cheng Kung University, 70101, Tainan, Taiwan.
A new series of biaryls, bi-linear-terphenylenes (BLTPs), were prepared using the tert-butyllithium-mediated cyclization as the key synthetic step. The three-dimensional structures of the studied compounds were verified using X-ray crystallography and DFT calculations. Tetraaryl(ethynyl)-substituted BLTPs are highly crowded molecules, and the internal rotation around the central C-C bond is restricted due to a high barrier (>50 kcal/mol).
View Article and Find Full Text PDFMolecules
November 2022
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Ave. 9, 630090 Novosibirsk, Russia.
Sterically shielded nitroxides, which demonstrate high resistance to bioreduction, are the spin labels of choice for structural studies inside living cells using pulsed EPR and functional MRI and EPRI in vivo. To prepare new sterically shielded nitroxides, a reaction of cyclic nitrones, including various 1-pyrroline-1-oxides, 2,5-dihydroimidazole-3-oxide and 4-imidazole-3-oxide with alkynylmagnesium bromide wereused. The reaction gave corresponding nitroxides with an alkynyl group adjacent to the N-O moiety.
View Article and Find Full Text PDFChem Asian J
August 2020
Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8551, Japan.
Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π-conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt-catalyzed cycloisomerization of the corresponding ethynyl-substituted precursors. The nonplanar and helical structure was confirmed by X-ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol .
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