Phosphorus ylides of cage-opened sulphide [60]fullerene derivatives

Abstract

The replacement of a ketone with a sulfide moiety changes the electronic properties of cage-opened fullerene ylides, thus causing a hypsochromic shift in absorption and a cathodic shift of reduction potentials.

Synthesis of an Open‐Cage C60 Derivative with a Double Stopper

“…[14] Though the reactivity of 1 is currently less studied, phosphorous-functionalization was found to proceed as in the case of the related open-cage C 60 derivatives (Figure 1). [13,15] In this work, we show the construction of a double stopper on 1 through a selective double reduction, revealing a kinetic stabilization of encapsulated Ar and N 2 .…”

“…From the integrated peak area, the ratio of H 2 O@2, N 2 @2 (+ empty 2), [2,3] and Ar@2 was determined to be 10, 14, and 76 %, respectively. By comparing the 13 C NMR spectrum (126 MHz, CS 2 /CDCl 3 (1 : 1)) with the simulated one at GIAO-B3LYP-D3/6-311G(d,p) (Figures 3b,S2,S9) for 2, two sp 3 signals at δ 78.57 and 72.13 ppm were assignable to C2 and C3, respectively. The two carbonyl signals at δ 196.46 and 181.07 were suggested to correspond to C4 and C1, respectively.…”

Synthesis of open-[70]fullerenes bearing huge orifices

“…We then examined the orifice enlargement of 3 by reductive sulfenylation. 11 Thus, an ODCB solution of 3 containing 1 equiv. of S 8 and 0.5 equiv.…”

“…of TDAE afforded 6 as a major product (58%), while 4 (8%) and 5 (9%) were also obtained as minor products. As is the case with open-[60]fullerenes, 11 6 is considered to be formed stepwise from 4 and 5 .…”

π-Extended Fullerenes with a Reactant Inside

“…For the facile π-extension of fullerenes, we focused on open-[60]­fullerene 1 bearing a 1,2-dicarbonyl moiety which would be a potential scaffold to extend its π-conjugation via tandem condensation reactions (Figure a). Thus, an o -dichlorobenzene (ODCB) solution containing 1 and excessive diamines were heated at 180 °C for 4 h in a sealed glass tube.…”