Topochemical Polymerization of Phenylacetylene Macrocycles: A New Strategy for the Preparation of Organic Nanorods

Abstract

Soluble organic nanorods were prepared from phenylacetylene macrocycles using the topochemical polymerization of butadiyne moieties placed both inside and outside the macrocycles' skeletons. Macrocycles containing amide groups were self-assembled in a columnar fashion through the formation of an organogel in ethyl acetate. Upon irradiation with UV light, the Raman signals associated with butadiyne units completely vanished, indicating the creation of covalently linked nanorods.

Improving the reactivity of phenylacetylene macrocycles toward topochemical polymerization by side chains modification

“…Unlike PAM1 , the presence of a columnar arrangement cannot be established from the diffractogram [31,39]. Instead, only a broad peak at 2θ = 20° was observed, indicating the presence of intramolecular liquid-like order between the alkyl chains [2].…”

“…Recently, many research groups used this strategy to design several types of π-conjugated monomers capable of hydrogen bonding to create nanowires [21–23], nanoparticles [24–27], nanotubes [28–31] and two-dimensional layered materials [32] from organogels. The key to success was to obtain a good balance between solubility and gelation properties.…”

“…Nonetheless, the polymerization of diyne units within PAMs to give covalent nanorods and nanotubes is very slow and gives low yields of polymerization, generally too low to be determined accurately [38–39]. In order to increase the efficiency of polymerization, the incorporation of external diyne chains on the PAMs core have been realized [31]. This design allowed us to increase the yield of polymerization to 15%.…”

Oligoyne Derivatives as Reactive Precursors for the Preparation of Carbon Nanomaterials

“…23 The strategy to prepare PDAwalled nanotubes from PAMs is presented in Scheme 6. 24,25 As for the linear polymers, nanoparticles, and nanowires, the preparation of PDA-walled nanotubes from PAMs required basic, but very important elements of design to ensure the efficient preparation of organogels and xerogels. The structures of the PAMs we prepared, PAM1 and PAM2, are shown in Scheme 6, part a.…”

Synthesis and properties of a trapezoid shaped macrocycle with different [n]yne units

“…7,8 Most recently, we reported the synthesis of rhomboidal macrocycles serving as a monomeric unit of graphdiyne-like nanoribbons (Fig. 1, le).…”