Synthesis and Solubility Properties of Methanofullerenes Containing Primary Ammonium Ion Functionalities

Abstract

The synthesis of novel methanofullerene derivatives bearing a primary ammonium ion functionality is described. They are obtained by a Bingel cyclopropanation reaction on C60 with malonate esters, bearing both a solubilizing poly(oxyethylene) chain and an aliphatic chain ending with a BOC‐protected amine. After removal of the protecting group, a counterion exchange methodology allows for the introduction of a perfluorinated anion, bringing the overall solubility of these derivatives to 98 mg/mL in an organic CH2Cl2 solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Synthesis and characterization of branched fullerene-terminated poly(ethylene glycol)s

“…Although NMR integration is more reliable for determination of actual abundance, it seems that MALDI peak intensity may also be used as a good approximation in the current system. The UV-vis spectra of PEG~4(OPCB) 2 (4), PEG~2 1 (OPCB) 3 (5) and PEG~1 5 (OPCB) 4 (6) products in toluene have three electronic absorption bands at 330, 433 and 510 nm (Figure 2a), similar to PCBM, as expected. The retention of the optoelectronic properties should be helpful for PV applications.…”

“…Thus, the average number of repeating units of each PEG compound was obtained from the integral ratio of the acyloxymethylene protons to the main PEG signals (see supporting information, Figure S3- 5), and found to be 4, 21 & 15 for bis-OH, tris-OH and tetrakis-OH terminated PEGs respectively. These 1 H NMR findings are consistent with the number average of molecular weight distributions in the MALDI spectra of the pure PEG cores (supporting information, Figure S8-9).…”

“…Similar to the preparation of 3-arm adducts of oligothienylenevinylenes and C 60 , 33 the yield of isolated PEG 24 (OPCB) 3 [8] and all other adducts were low, even though the reaction medium was saturated with PCBM. 29 The final yields of fully substituted products were 4 % for PEG~2 1 (OPCB) 3 [5], 8 % for PEG~1 5 (OPCB) 4 [6] and 5 % for PEG 24 (OPCB) 3 [8]. In the case of PEG~1 5 (OPCB) 4 [6], the presence of a minor 3-arm PEG impurity in the starting material may have affected the overall yield of the reaction.…”

“…Due to its unique optoelectronic properties, and phase behaviour, fullerene [60] is one of the most commonly used materials in the preparation of polymer donor-acceptor bulk heterojunction (BHJ) solar cells. [1][2][3][4] However, the low solubility and processability of fullerenes in organic solvents has limited their direct use in solution and encouraged the development of a wide range of functionalised derivatives, including methanofullerenes [5][6][7][8][9] and fulleropyrrolidines. 10,11 These functionalised derivatives offer significant increases in solubility and processability while preserving the important electronic and optical properties of the parent fullerenes.…”

Antimicrobial Photodynamic Therapy with Functionalized Fullerenes: Quantitative Structure-activity Relationships

“…Several fullerene derivatives that have amine groups present have been reported. However, in all cases, the amine is either separated from the fullerene core by a rigid linker [25, 26], or is only reported in the trifluoroacetate salt form [27, 28]. Notably missing from the literature is a report of a free basic amine attached to the fullerene core with a short, flexible linker.…”