Y.F.Wang

The nucleophilic addition of phosphites to a cage‐opened fullerene C₆₀ derivative gave α‐hydrophosphates and enol phosphates as kinetic and thermodynamic products, respectively. Different from classical Abramov reactions, which give phosphonates bearing a P−C bond, these products possess a P−O bond. Theoretical calculations suggested that the charge delocalization of zwitterionic intermediates along with the π‐framework facilitate the phospha‐Brook rearrangement, thus forming nonclassical Abramov products. More information can be found in the Communication by Y. Murata et al. (DOI: 10.1002/chem.202004035).

Contrary to classical Abramov reactions, which give phosphonates bearing a P−C bond, the nucleophilic addition of phosphites to conjugate macrocyclic orifices on cage‐opened C₆₀ derivatives resulted in the formation of phosphates bearing a P−O bond via phospha‐Brook rearrangement as a key step.

Abstract

By nucleophilic addition of phosphite P(OMe)₃ to a cage‐opened C₆₀ derivative, α‐hydrophosphate and enol phosphate were obtained as kinetic and thermodynamic products, respectively. Different from classical Abramov products bearing a phosphorus–carbon bond, these products have a phosphorus–oxygen bond. The observed anomaly originates from the fully conjugated π system, which significantly stabilizes zwitterionic intermediates bearing a phosphorus–oxygen bond. The thus formed enol phosphate was found to exhibit an intense absorption band that extended to 730 nm, reflecting the intramolecular charge‐transfer transitions. We also report domino phosphorylation reactions, which gave a cage‐opened C₆₀ derivative bearing a direct P−C bond.

Ruling pentagons: The ¹³C NMR spectrum and unique aromatic features of C _2v C₆₆H₄, in which three π‐aromatic circuits are present at the bottom boat section of this fullerene derivative, are compared with those of pristine C₆₀, employing DFT calculations.

Abstract

The isolated‐pentagon rule (IPR) is a determining structural feature that accounts for hollow fullerene stabilization and properties related to C _n (n≥60) cages. The recent characterization of an unprecedented non‐IPR hydrofullerene, C _2v C₆₆H₄, bearing two heptagons with adjacent fused‐pentagon motifs, largely dismisses this feature. Herein, employing DFT calculations, the ¹³C NMR spectroscopy and aromatic behavior of C _2v C₆₆H₄ are explored. The results show the presence of three π‐aromatic circuits at the bottom boat section of C₆₆H₄, indicating the unique features of this hydrofullerene in comparison to those of pristine C₆₀. In addition, under specific orientations of the external field, certain π‐aromatic circuits are enabled, resulting in a more aromatic fullerene than that of C₆₀, but lower than that of the spherical aromatic C₆₀ ⁶⁻ fulleride. Notably, under a field aligned with the saturated carbon atoms, nonaromatic characteristics are exposed. This reveals that spherical‐like cages can involve a complex magnetic response that heavily depends on the orientation of the applied field.

Oh, now I see! The precipitates formed during Th^IV hydrolysis are ThO₂ nanoparticles, which in their initial stages of formation are a mixture of ultra‐small nanoparticles and Th hexamer clusters. This new structural insight is made possible by the combined use of two synchrotron techniques: HEXS and XANES in HERFD mode, which probe short‐ and medium‐range order in the sample under study. More information can be found in the Full Paper by L. Amidani et al. on page 252.

In their concept article on page 12, X. Cui, A. P. van Muyden, and P. J. Dyson, describe state‐of‐the‐art core–shell materials employed as heterogeneous catalysts for a range of sustainable catalytic transformations, focusing on the advantages that this intriguing class of catalysts brings to the field.

This Review discusses synthetic approaches to fullerene‐based hybrids with low‐dimensional (LD) materials and their properties. Recent advances in the design of fullerene‐based LD nanomaterials for (photo)electrocatalytic applications are emphasized. The relationship between the electronic structures and the catalytic functions of the heterostructures is addressed to provide an understanding of these emerging materials at the molecular level.

Abstract

An emerging class of heterostructures with unprecedented (photo)electrocatalytic behavior, involving the combination of fullerenes and low‐dimensional (LD) nanohybrids, is currently expanding the field of energy materials. The unique physical and chemical properties of fullerenes have offered new opportunities to tailor both the electronic structures and the catalytic activities of the nanohybrid structures. Here, we comprehensively review the synthetic approaches to prepare fullerene‐based hybrids with LD (0D, 1D, and 2D) materials in addition to their resulting structural and catalytic properties. Recent advances in the design of fullerene‐based LD nanomaterials for (photo)electrocatalytic applications are emphasized. The fundamental relationship between the electronic structures and the catalytic functions of the heterostructures, including the role of the fullerenes, is addressed to provide an in‐depth understanding of these emerging materials at the molecular level.

The formation of three‐dimensional micro‐cubes and micro‐dice of C₇₈ via a facile liquid–liquid interfacial precipitation method is systematically studied. The cubic microstructures are readily transformed into dice‐like microstructures by simply shaking the solution. More importantly, both microstructures exhibit photoelectrochemical and photoluminescence properties, indicating potential applications of such higher fullerenes in optoelectronic devices.

Abstract

The single‐crystal micro/nanostructures of fullerene species, namely C₆₀ and C₇₀, have been previously studied, but studies on the morphology and properties of higher fullerenes have rarely been reported due to the limited amount of samples and their ellipsoidal isomeric structures. Herein, we report the formation of three‐dimensional (3D) micro‐cubes and micro‐dice of a higher fullerene (C₇₈) via a facile liquid–liquid interfacial precipitation (LLIP) method. The micro‐cubes were prepared by regulating the concentration of C₇₈ in trimethylbenzene (TMB) and the volume ratio of TMB and isopropanol. Interestingly, the micro‐cubes are transformed into micro‐dice with an open‐hole on each crystal face by simply shaking the solution. X‐ray diffraction and Fourier‐transform infrared spectroscopic studies revealed a simple cubic unit cell with a lattice constant of 10.6 Å and intercalated TMB molecules in both crystals. The C₇₈ cubic and dice‐like microstructures exhibited enhanced photoelectrochemical and photoluminescence properties compared with pristine C₇₈ powder, indicating their potential applications as photodetectors and photoelectric devices.

Nature Communications, Published online: 03 August 2020; doi:10.1038/s41467-020-17684-6

The synthesis of hydrocarbons with attractive electronic structures remains challenging. Here, the authors describe the synthesis and properties of the C70 fragment as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, which exhibits near-infrared (NIR) absorption.

Situated in the historical and picturesque city of Suzhou, a metropolis well reputed in the world for its classic gardens, Soochow University (SU) was founded in 1900 and represents one of the first modern universities in China. Soochow University is a top comprehensive university in Jiangsu Province, listed as a key university of “Project 211” and a member of “the Double First-Class” Initiative.

The College of Chemistry, Chemical Engineering and Materials Science grew out of the Chemistry Department of Soochow University, which was founded in 1914 and was one of the earliest chemistry departments in China. The chemistry research at SU focuses on precision synthesis, micro/nano materials for environmental science, energy and materials, health chemistry and diagnosis, precision catalysis and application as well as green chemistry and chemical engineering. As a result of the scientific and technological innovation strategy “Think Big and Start Small”, Soochow University has harvested fruitful results in chemistry innovation. As indicated by data from Nature Index and Lens in 2017, the field of chemistry at Soochow University headed the list of mainland universities among the global innovative scientific research institutions and universities. Noticeably, both the disciplines of Chemistry and Materials Science at the College are listed in the top 1‰ around the world according to the latest Essential Science Indicators (ESI).

“Following the rapid developments in new technology and equipment, today we are living in a golden age of chemistry.” says Prof. Jianlin Yao, Dean of the College of Chemistry, Chemical Engineering and Materials Science, Soochow University. “Soochow University chemists will continue to work on original innovation, breakthrough techniques and technology transfer in practical application, and all of us are committed to the sustainable development goals of humanity.”

To celebrate the 120^th anniversary, we are sharing a special virtual issue of research articles from Soochow University chemists. Authors across the university have contributed more than 60 articles on topics ranging from synthetic chemistry to biological chemistry and other cross chemistry disciplines. We hereby invite you to read through these selected articles to witness the achievements made by Soochow University in the past few years (2015-2020).

Find the collection online here!

Jianlin Yao

Soochow University

Nature Communications, Published online: 03 August 2020; doi:10.1038/s41467-020-17684-6

The synthesis of hydrocarbons with attractive electronic structures remains challenging. Here, the authors describe the synthesis and properties of the C70 fragment as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, which exhibits near-infrared (NIR) absorption.

By incorporating azobenzene photochromic units in the double functionalization of [60]fullerene, the regiochemistry of the double cyclopropanation reaction could be controlled by using either the E or the Z isomeric forms of the photoswitch. Once covalently linked to the C₆₀ sphere, the azobenzene unit changes its light‐ and thermally‐induced isomerization properties.

Abstract

Multi‐functionalization and isomer‐purity of fullerenes are crucial tasks for the development of their chemistry in various fields. In both current main approaches—tether‐directed covalent functionalization and supramolecular masks—the control of regioselectivity requires multi‐step synthetic procedures to prepare the desired tether or mask. Herein, we describe light‐responsive tethers, containing an azobenzene photoswitch and two malonate groups, in the double cyclopropanation of [60]fullerene. The formation of the bis‐adducts and their spectroscopic and photochemical properties, as well as the effect of azobenzene photoswitching on the regiochemistry of the bis‐addition, have been studied. The behavior of the tethers depends on the geometry of the connection between the photoactive core and the malonate moieties. One tether lead to a strikingly different adduct distribution for the E and Z isomers, indicating that the covalent bis‐functionalization of C₆₀ can be controlled by light.