Tunable Epoxidation of Single‐Walled Carbon Nanotubes by Isolated Methyl(trifluoromethyl)dioxirane

Abstract

Organic functionalization of carbon nanotube sidewalls is a tool of primary importance in material science and nanotechnology, equally from a fundamental and an applicative point of view. In this paper, a mild and easily tunable approach to the sidewall decoration of single-walled carbon nanotubes (SWCNTs) with epoxides and their subsequent derivatization (ring opening) upon treatment with reactive nucleophiles is presented. The treatment of HiPco purified SWCNTs with dioxirane solutions results in highly oxidized CNTs, which are used as electrophilic platforms for their successive derivatization/functionalization. As a result of the choice of accessible, easy to handle and store dioxiranes, multiple oxidation cycles could be performed on the same sample, thus allowing for a final improvement in the extent of oxidation at the CNT sidewall

Synthesis, Supramolecular Behavior, and In Vitro Photodynamic Activities of Novel Zinc(II) Phthalocyanines “Side‐strapped” with Crown Ether Bridges

“…In the cases of 3a and 3a′ the calculated weight losses at 450 °C are in the same range (4 and 3.3 %, respectively) whereas derivative 4 presented a significant loss (8.7 %, without allowance for the weight loss related to the precursor 3a ), which corresponded to a functionalization of 750 μmol g –1 with hexamethylenediamine, presumably introduced by opening of the epoxide rings. The oxidized derivatives 3a and 3a′ present an interesting difference in stability at higher temperatures: whereas 3a presents a weight loss of 10.9 % at 580 °C, with behavior similar to that of the analogue obtained with SWCNTs27 and also evident in the case of derivative 4 , compound 3a′ proves to be more stable. The latter compound shows a weight loss of 4.6 % (at 580 °C, absolute value), suggesting that the treatment with 2,2,2‐trifluoroacetophenone and H 2 O 2 might introduce functionalization without excessively affecting the carbon skeletons of the tubes, the thermal stability of which is higher.…”

“…The ox ‐MWCNT samples are reactive platforms for successive functionalization/derivatization, and a model reaction protocol has been set up 27. In view of the ability of epoxides to undergo nucleophilic attack with subsequent ring opening, the reaction between ox ‐MWCNT and an aliphatic diamine was investigated.…”

“…We have shown recently that the facile epoxidation of SWCNTs can be carried out by treatment with isolated methyl(trifluoromethyl)dioxirane (TDFO, 1b , Figure 1). 27 Indeed, the efficient epoxidation of simple and/or structurally complex alkenes under mild and neutral conditions is the highlight of the chemistry of these oxidants, and can be successfully applied as an easily tunable approach to the sidewall decoration of SWCNTs with epoxides and their subsequent derivatization (ring opening) upon treatment with reactive nucleophiles.…”

“…As discussed above, the most promising organic oxidants for efficient epoxidation of alkenes include perhydrates26 and dioxiranes 27,28. These reagents are derived from ketones in conjunction with an oxygen source.…”

Preparation and Characterization of Soybean Oil-Based Polyurethanes for Digital Doming Applications

“…Our twenty years’ experience in green chemistry [18,19,20,21,22,23] has convinced us to extend our studies to the synthesis of bio-polyurethanes [24]. In fact, in our recent work we just reported an efficient, cost-effective, and environmentally safer conversion of soybean oil (SO) into soy-based PU, using as catalyst the molybdenum(VI) dichloride dioxide (MoCl 2 O 2 ) for one-pot synthesis starting from the epoxidized oil (ESO) and with 2,6-tolyl-diisocyanate (TDI).…”