Authors: Chen, Bin
Holstein, Julian J.
Horiuchi, Shinnosuke
Hiller, Wolf G.
Clever, Guido H.
Title: Pd(II) coordination sphere engineering: pyridine cages, quinoline bowls, and heteroleptic pills binding one or two fullerenes
Language (ISO): en
Abstract: Fullerenes and their derivatives are of tremendous technological relevance. Synthetic access and application are still hampered by tedious purification protocols, peculiar solubility, and limited control over regioselective derivatization. We present a modular self-assembly system based on a new low-molecular-weight binding motif, appended by two palladium(II)-coordinating units of different steric demands, to either form a [Pd2L14]4+ cage or an unprecedented [Pd2L23(MeCN)2]4+ bowl (with L1 = pyridyl, L2 = quinolinyl donors). The former was used as a selective induced-fit receptor for C60. The latter, owing to its more open structure, also allows binding of C70 and fullerene derivatives. By exposing only a fraction of the bound guests’ surface, the bowl acts as fullerene protecting group to control functionalization, as demonstrated by exclusive monoaddition of anthracene. In a hierarchical manner, sterically low-demanding dicarboxylates were found to bridge pairs of bowls into pill-shaped dimers, able to host two fullerenes. The hosts allow transferring bound fullerenes into a variety of organic solvents, extending the scope of possible derivatization and processing methodologies.
Subject Headings: Supramolecular chemistry
Self assembly
Coordination cage
Coordination bowl
Fullerene separation
Issue Date: 2019-05-08
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Appears in Collections:Lehrstühle für Anorganische Chemie

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