Linking Two Holey [60]Fullerenes

Synthetic holey [60]fullerene dimers exhibited strong electronic communication between cags, giant dissymmetry factor, and heterochiral recognition.
Published in Chemistry
Linking Two Holey [60]Fullerenes
Like

Share this post

Choose a social network to share with, or copy the shortened URL to share elsewhere

This is a representation of how your post may appear on social media. The actual post will vary between social networks

Natural carbon allotropes adopt a variety of topologies depending upon bond connection modes of carbon atoms, thus generating different shapes and dimensionalities such as sphere (fullerene, 0D), tubular (nanotube, 1D), and sheet (graphene, 2D). Coalescence of fullerenes is a fundamental thinking model when one aims to construct carbon allotropes that are otherwise unavailable in nature. A minimum unit of coalesced fullerenes is a fullerene dimer. Hence, organic chemists have continuously paid considerable attention for synthesizing and structurally characterizing fullerene dimers such as (C60)2 and (C59N)2, in which two fullerene cages are linked by one or two single bonds, consequently disconnecting π-conjugation between the two cages. In contrast, coalesced fullerene dimers with full π-conjugation have been found only as transiently-producible species in a physical process under high electron voltage through TEM (transmission electron microscopy). Since serial coalescence of fullerenes has been believed to reach long-envisioned hypothetical fullerene-based nanomaterials, such as fullerene sponge or fullerites, it is of particular importance to set a rational strategy toward synthetic interfullerene allotropes. 

In the paper "Synthesis of inter-[60]fullerene conjugates with inherent chirality" recently published in Nature Communications, we focused on holey [60]fullerenes with functional groups on their hole. This type of fullerenes is usually called as open-[60]fullerenes which are π-conjugated hosts utilized in supramolecular single-molecule science as well as electron acceptors in solar cell application. Importantly, open-[60]fullerenes possess inherent chirality (fullerene chirality) which was very recently witnessed as the third function of them and potentially shows better chiroptical activities than most chiral organic materials. Thus, our goal had been set to get an inherently-chiral synthetic interfullerene conjugate. Owing to high designability on molecular and electronic structures of open-[60]fullerenes, we finally achieved the synthesis of non-conjugated and conjugated chiral inter-[60]fullerene hybrids via a phosphine-mediated one-pot deoxygenative C=C bond formation (please see details in manuscript) where the key intermediate is 1-phosphonium-3-carbabetaine (see Behind The Paper and Commun. Chem. 20203, 90.). Reflecting the inherent chirality of the open-[60]fullerene, the non-conjugated inter[60]fullerene hybrid exhibited characteristic heterochiral recognition whose structure was crystallographically and spectroscopically determined. In addition, the inter-[60]fullerene conjugate showed strong intercage interactions during 6-electrons uptake as well as excellent chiroptical activity with a gigantic dissymmetry factor of 0.21 which breaks the record of known chiral organic molecules. 

Synthetic inter-[60]fullerene hybrids

Yoshifumi Hashikawa,* Shu Okamoto & Yasujiro Murata* 
Synthesis of inter-[60]fullerene conjugates with inherent chirality.
Nat. Commun. 2024, 15, 514.
DOI: 10.1038/s42004-020-00340-x
More details in Nature Communications via https://www.nature.com/articles/s41467-024-44834-x
Our research group: https://www.scl.kyoto-u.ac.jp/~kouzou/en/index.html

Please sign in or register for FREE

If you are a registered user on Research Communities by Springer Nature, please sign in

Follow the Topic

Organic Chemistry
Physical Sciences > Chemistry > Organic Chemistry

Related Collections

With collections, you can get published faster and increase your visibility.

Cancer and aging

This cross-journal Collection invites original research that explicitly explores the role of aging in cancer and vice versa, from the bench to the bedside.

Publishing Model: Hybrid

Deadline: Jul 31, 2024

Applied Sciences

This collection highlights research and commentary in applied science. The range of topics is large, spanning all scientific disciplines, with the unifying factor being the goal to turn scientific knowledge into positive benefits for society.

Publishing Model: Open Access

Deadline: Ongoing