Three‐Dimensional Metal–Fullerene Frameworks

Abstract

Hexakis-substituted [60]fullerene adducts with icosahedral symmetry provide an unprecedented scaffold for the spatial arrangement of twelve functional groups with high geometric precision. This unique molecular symmetry identifies such polyfunctional organic building blocks as potential highly connective linkers for coordination polymer and metal-organic framework synthesis. Hereby, the linker exhibits a higher connectivity than the metal ions and with the main connectivity based on the ligand, this can create a new type of inversely cross-linked framework. Two hexakis adducts bearing either twelve glycolic acid or 3-hydroxypropionic acid side chains attached to its malonate units were incorporated as organic connectivity centers in the first fullerene-containing three-dimensional frameworks by coordination with Zn(2+) .

Hexakis [60]Fullerene Adduct‐Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties

“…A new organo‐soluble C 60 hexa‐adduct bearing twelve thiocyanate functions has been used as a stabilizing/assembling agent to assemble homogeneous 3 nm Au NPs into apparently extended tridimensional networks . Hexakis‐substituted [60]fullerene adducts have been recently identified as potential highly connective linkers for coordination polymers and metal–organic framework synthesis …”

Supramolecular frameworks based on [60]fullerene hexakisadducts

“…1) revealing a complex hydrogen-bonding network in the crystalline state [57]. Based on this initial finding, we also utilized C2 and elongated derivative C3 as organic connectivity centers in metal-organic assemblies obtained after reaction with Zn 2+ ions [55], however, no crystal structure of metal-free C3 has been reported yet. As a general packing motif for all fullerene-containing frameworks, the individual carbon building blocks are arranged in face centered cubic (fcc) packing with the distances between the molecules depending on the spacer length and the mode of cross-linking.…”

“…Hexakisadduct C3 [55] and malonate 1 [59] were synthesized according to literature procedures. X-ray crystallography: Bruker D8 Quest diffractometer with Photon 100 CMOS APS detector and Montel multilayer optics monochromated Cu K α radiation.…”

Synthesis of Metal Complexes with an Open‐Cage Fullerene as the Ligand

“…[2] Attaching classical coordination ligands to the fullerene cage through covalent bonds is another common method for making fullerenec ontaining metalc omplexes. [3] Amongt hem, fullerened erivatives with attachedp orphyrins have been wells tudied. [4] Interaction between the fullerene cage and the porphyrin metal centerc an be tuned by the length and nature of the linker covalently bonded to the fullerenec age.…”