Synthesis of Fullerene Adducts with Terpyridyl‐ or Pyridylpyrrolidine Groups in trans‐1 Positions

Abstract

Two C(60) hexakis-adducts (2 and 3) were synthesized by using a protection-deprotection strategy. The symmetric fullerene tetrakis-adduct 8 was obtained by anthracene removal from the hexakis-adduct 7. Reaction of 8 with terpyridylglycine or pyridylglycine afforded two hexakis-adducts, 2 and 3. By using the retro-cyclopropanation reaction, the four malonate addends located on the equatorial belt of the hexakis-adducts were removed to afford two trans-1 bis-adducts, 4 and 5, with terpyridyl- or pyridylpyrrolidine groups. The structures of 2 and 3 were confirmed by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and (1)H, (13)C, and COSY NMR, and UV-visible spectroscopy. The cyclic voltammograms of fullerene multiadducts 2, 3, and 9 show irreversible reductions. Self-assembled monolayers (SAMs) of 1 and 3 were formed on gold surfaces through nitrogen adsorption. SAMs of 3 represent the first example of a fullerene hexakis-adduct formed on gold surfaces through nitrogen adsorption. Controlled potential electrolyses (CPE) were conducted to prepare trans-1 bis-adducts 4 and 5 modified with terpyridyl and pyridyl groups.

TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

“…The close to reversible system of redox peaks at 0.81 V is attributed to the TEMPO/TEMPO + redox couple (Krukowski et al 2009), thus confirming the presence of nitroxyl radicals on the surface of the synthesized C 60 fullerene derivative. As expected for its hexakis adduct, one main reduction signal is present in the corresponding CV curve (Zhang et al 2006). This signal was notably shifted toward negative potentials comparing to the values registered for pristine C 60 fullerene (Piotrowski et al 2013), allowing us to conclude that II has significantly lower electron accepting properties when compared to the unmodified C 60 core.…”

Design, Synthesis, and X‐Ray Crystal Structure of a Fullerene‐Linked Metal–Organic Framework

“…Different combinations of metal centers and organic ligands have resulted in elaborate designs with interesting structures and properties. The previously reported tetrakis[di(ethoxycarbonyl)methano]-C 60 (1) [17] was used as a starting material and reacted with 4,4'-(4,4'-(diazomethylene)bis(4,1-phenylene))dipyridine (2) (see Figure 1. [9] The spherical shape, high degree of symmetry, and coordinating geometries of C 60 make it an ideal candidate for the construction of supramolecular architectures.…”

“…The previously reported tetrakis[di(ethoxycarbonyl)methano]-C 60 (1) [17] was used as a starting material and reacted with 4,4'-(4,4'-(diazomethylene)bis(4,1-phenylene))dipyridine (2) (see Figure 1. The previously reported tetrakis[di(ethoxycarbonyl)methano]-C 60 (1) [17] was used as a starting material and reacted with 4,4'-(4,4'-(diazomethylene)bis(4,1-phenylene))dipyridine (2) (see Figure 1.…”

Soccer goes BOXing: Synthetic access to novel [6:0] hexakis[(bisoxazolinyl)methano]fullerenes

“…Later, his group extended this strategy to bis(4-phenyl-2-oxazoline) derivatives bearing an inherently chiral [3:3] hexaaddition pattern and used these structures as auxiliaries in stereoselective cyclopropanation reactions25. Related systems have also been published by Echegoyen26 and Rubin27.…”