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Creation of Highly Elaborated π-Space with Novel Nanocarbon Material and Extending Its Functionality

Posted: Sep. 11, 2014

Award Recipient: Emeritus Prof. Takeshi Akasaka Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba

Dr. K. Akasaka has accomplished leading research in nanocarbon systems such as fullerene, endohedral metallofullerene, and carbon nanotube. His major research achievements will be introduced hereinafter.

1. Molecular conversion of fullerenes
Fullerenes, new carbon allotropes, are a very attractive group of substances as a new cage type carbon material that exhibits various intriguing physical and chemical properties attributable to their particular and novel molecular structure. As basic research of "Chemistry outside and inside of the fullerene spherical surface", Dr. Akasaka started research while devoting attention to the importance of a functional group of fullerenes using organosilicon compounds by way of an organic chemistry approach for the first time in the world, identified intriguing molecular structures of various fullerene derivatives, and succeeded in adding new electronic characteristics, thereby giving a significant impact to the entire field. Furthermore, he discovered that activation of fullerene using light is effective. He developed a new research field for molecular conversion in fullerene chemistry.

2. Development of endohedral metallofullerene chemistry
Since the discovery of fullerene, attempts to capsulate metallic atoms, rare gas, nitrogen atoms, etc. into a space in its carbon cage have been carried out actively. Although endohedral metallofullerene incorporating metallic atoms has been attracting great interest as a substance having novel electronic characteristics resulting from electron transfer from metallic atoms to carbon cages as well as its peculiar structure, a persistent problem for their further development is that the amount of production and isolation of this substance is scarce. Dr. Akasaka established a technology for large-volume synthesis and dispensing of endohedral metallofullerene, then carried out research related to molecular structure and electronic characteristics of endohedral metallofullerene for the first time in the world, which are now regarded as breakthrough studies. He developed a world of highly elaborated π-space using structures and functions attributable to the specific nature and diversity of endohedral metallofullerene. He discovered an additional regioselective reaction that is extremely important for the chemical modification of endohedral metallofullerene. This discovery contributed greatly to the progress of endohedral metallofullerene chemistry, where dynamic behaviors of encapsulated metallic atoms, which are enclosed by a carbon cage and which can not be touched directly from outside, are controlled by chemical modification. Dynamic control and control of the addition position of encapsulated metallic atoms using a reversible addition reaction suggest the possibility of their application to the creation of various functionalized molecules. He also succeeded in the synthesis, isolation, structural determination, and elucidation of electronic characteristics of previously unheard of novel fullerenes incorporating carbide clusters. This is the dawn of fullerene chemistry incorporating carbide. Although it was believed at that time that there were many missing metallofullerenes such as La@C72 and La@C74 not isolated yet in the soot and that they have unknown properties differing from those of ordinary fullerenes, he extracted La@C72 and La@C74 in the form of dichlorophenyl adduct using 1,2,4-trichlorobenzene. This research achieved a breakthrough in this field. The isolation, structural determination, and elucidation of electronic characteristics of many missing metallofullerenes were promoted. Therefore, categorical structural analysis of diverse endohedral metallofullerenes was performed thoroughly, establishing the foundation of endohedral metallofullerene research. Challenges to supramolecular systems using endohedral metallofullerene by Dr. Akasaka had a significant impact on the research field of endohedral metallofullerenes as one development of endohedral metallofullerene functions: he made a breakthrough in that field for the first time in the world. This accomplishment suggested the possibility of construction of a functional supramolecular system and development into photoelectric conversion material. In addition, he succeeded in creating a nanorod structure of endohedral metallofullerene adduct and discovered that it has high charge conveyance characteristics, which suggests that for realization of application of organized endohedral metallofullerene, it is important to control the position and orientation of addition by chemical modification. These studies are extremely important achievements in the increasingly important study of nanoscience.

3. High dispersion and separation of single-walled carbon nanotubes
Carbon nanotubes (CNTs) are currently attracting attention as a new nanocarbon material anticipated for application as conducting materials and other materials. For sufficient utilization of electric characteristics of CNT, the metallic nature and semiconductivity of CNTs should be used independently. The development of selective synthesis methods and separation methods of this material were urgent issues. Dr. Akasaka led the world's researchers in developing a high dispersion method for CNTs using the interaction between molecules with amine and succeeded in the efficient separation of metallic CNTs with excellent conductivity in a nondestructive manner. Nondestructive separation of metallic and semiconductor nanotube using supramolecular chemistry achieved a breakthrough in CNT chemistry.

As described above, Dr. Akasaka performed significant achievements in the nanoscience field using an organic chemistry approach. In the research of π-space chemistry by nanocarbon systems such as fullerene, endohedral metallofullerene, and carbon nanotubes, he played a leading role in the development of this field. The fact that these results had ripple effects on molecular design in theoretical research and methodology of property assessment has been greatly appreciated at home and abroad. As described above, Dr. Akasaka played a pioneering role in the broad range of π-space chemistry field from basic chemistry to application. The Chemical Society of Japan has recognized that his achievements are worthy of the society's award.