Lithium-Mediated Mechanochemical Cyclodehydrogenation.

Cyclodehydrogenation is an essential synthetic method for the preparation of polycyclic aromatic hydrocarbons, polycyclic heteroaromatic compounds, and nanographenes. Among the many examples, anionic cyclodehydrogenation using potassium(0) has attracted synthetic chemists because of its irreplaceable reactivity and utility in obtaining rylene structures from binaphthyl derivatives. However, existing methods are difficult to use in terms of practicality, pyrophoricity, and lack of scalability and applicability. Herein, we report the development of a lithium(0)-mediated mechanochemical anionic cyclodehydrogenation reaction for the first time. This reaction could be easily performed using a conventional and easy-to-handle lithium(0) wire at room temperature, even under air, and the reaction of 1,1'-binaphthyl is complete within 30 min to afford perylene in 94% yield. Using this novel and user-friendly protocol, we investigated substrate scope, reaction mechanism, and gram-scale synthesis. As a result, remarkable applicability and practicality over previous methods, as well as limitations, were comprehensively studied by computational studies and nuclear magnetic resonance analysis. Furthermore, we demonstrated two-, three-, and five-fold cyclodehydrogenations for the synthesis of novel nanographenes. In particular, quinterrylene ([5]rylene or pentarylene), the longest nonsubstituted molecular rylene, was synthesized for the first time.

Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity of Atomic Nitrogen.

To investigate the intrinsic reactivity of atomic nitrogen, which had previously been accomplished only by examining its decay in the gas phase using special equipment, a nitrogen atom was inserted into a series of molecule-encapsulating C60 and C70 fullerenes. Among the studied endofullerenes, H2 @C70 was able to encapsulate an additional nitrogen atom within the fullerene cage under radiofrequency plasma conditions. The product was analyzed by ESR spectroscopy and mass spectrometry in solution, which revealed that the nitrogen atom with a quartet ground state does not react but weakly interact with the H2 molecule, thus demonstrating the utility of such fullerenes as "nanoflasks".

X-ray observation of a helium atom and placing a nitrogen atom inside He@C60 and He@C70.

Single crystal X-ray analysis has been used as a powerful method to determine the structure of molecules. However, crystallographic data containing helium has not been reported, owing to the difficulty in embedding helium into crystalline materials. Here we report the X-ray diffraction study of He@C60 and the clear observation of a single helium atom inside C60. In addition, the close packing of a helium atom and a nitrogen atom inside fullerenes is realized using two stepwise insertion techniques, that is, molecular surgery to synthesize the fullerenes encapsulating a helium atom, followed by nitrogen radio-frequency plasma methods to generate the fullerenes encapsulating both helium and nitrogen atoms. Electron spin resonance analysis reveals that the encapsulated helium atom has a small but detectable influence on the electronic properties of the highly reactive nitrogen atom coexisting inside the fullerene, suggesting the potential usage of helium for controlling electronic properties of reactive species.

Synthesis and photovoltaic properties of acceptor materials based on the dimerization of fullerene C60 for use in efficient polymer solar cells.

We demonstrate that dimeric fullerene derivatives work as an excellent n-type material for polymer solar cells in combination with P3HT or PTB7, showing the best PCE of 3.3% or 6.1%, respectively. The device performance was influenced by the position of the two C60 moieties linked together.

Modification of the σ-framework of [60]fullerene for bulk-heterojunction solar cells.

Modification of the σ-framework of [60]fullerene has been shown to be a new avenue toward n-type materials for bulk-heterojunction solar cells. This approach allowed distinct control of the LUMO level of the C(60)π-system and resulted in a clear improvement of an open-circuit voltage.

Rational synthesis, enrichment, and (13)C NMR spectra of endohedral C(60) and C(70) encapsulating a helium atom.

Endohedral fullerenes encapsulating a helium atom, i.e., He@C(60) and He@C(70), at occupation levels of 30% were prepared by rational chemical synthesis. The existence of weak interactions between the inner helium and the outer fullerene cages was demonstrated by experimental and computational investigations.

Synthesis and reaction of fullerene C70 encapsulating two molecules of H2.

New endohedral fullerene C(70) encapsulating one and two H(2) molecule(s) has been synthesized by organic reactions, the so-called "molecular surgery" method, and the first organic derivatization of H(2)@C(70) and (H(2))(2)@C(70) has been conducted. Although the interaction between inner H(2) and outer C(70) is rather weak, (H(2))(2)@C(70) exhibits smaller equilibrium constants in the Diels-Alder reaction with 9,10-dimethylanthracene than those of H(2)@C(70).