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Self-Assembled Fullerene Nanostructures Lok Kumar Shrestha1＊ , Rekha Goswami Shrestha2, Jonathan P

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Self-Assembled Fullerene Nanostructures Lok Kumar Shrestha1＊ , Rekha Goswami Shrestha2, Jonathan P Journal of Oleo Science Copyright ©2013 by Japan Oil Chemists’ Society J. Oleo Sci. 62, (8) 541-553 (2013) REVIEW Self-Assembled Fullerene Nanostructures Lok Kumar Shrestha1＊ , Rekha Goswami Shrestha2, Jonathan P. Hill1 and Katsuhiko Ariga1, 3 1 World Premier International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044 JAPAN 2 ‌Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science 2641 Yamazaki, Noda, Chiba 278- 8510, JAPAN 3 PRESTO & CREST, JST, 1-1 Namiki, Tsukuba 305-0044 JAPAN Abstract: This review briefly summarizes recent developments in fabrication techniques of shape-controlled nanostructures of fullerene crystals across different length scales and the self-assembled mesostructures of functionalized fullerenes both in solutions and solid substrates. Key words: ‌fullerene, self-assembly, nanostructures, liquid-liquid interfacial precipitation, nanowhiskers, nanotubes, nanosheets 1 INTRODUCTION compose an icosohedra（l Ih）symmetric closed cage struc- Design of nanostructured materials whose properties ture of the C60 molecule（diameter～0.8 nm）. In C60, each can be tailored across different length scales so that they carbon atom is bonded to three other carbon atoms can be utilized in different functional systems and nanode- through sp2 hybridized bonds with the tendency for double vices fabrication is a current topic of great interest in the bonds not to be present at the pentagonal rings resulting in field of materials nanoarchitectonics. Self-assembly is one poor electron delocalization, i.e. C60 is not a superaromatic of the special techniques applied for the organization of molecule. As a result, it behaves as an electron deficient functional molecules such as fullerenes, amphiphiles, pro- molecule. The electron-accepting capability of C60 both in teins and peptides with molecular level precision in the solid state and solution have permitted special uses in the preparation of functional systems. This technique enables formation of charge-transfer complexes and bulk hetero- the arrangement of building blocks into a variety of nano- junctions with suitable donors for the production of photo- structures on the micro to macroscopic length scales. current. The formation of charge-transfer salts with a Using the concept of materials nanoarchitectonics in com- number of donor groups or doping with metals has led to 4） 5） bination with self-assembly, various building units have ferromagnetic or superconducting materials . C60 exhibits been assembled or organized/reorganized into hierarchic strong absorption bands in the UV region and weaker but functional nanostructures. Assembly of the ideal zero-di- significant bands in the visible region. Functionalized C60 mensional building block fullerene（C60）into higher dimen- retains these characteristics but, in addition, the absorp- sional crystalline nanostructures and assembly of function- tion of the derivatives extends further into the near-IR alized fullerenes into different mesostructures are good region demonstrating that C60 and its derivatives are very examples of the materials nanoarchitectonics concept. easily excited by low-energy light. This, combined with the 1） Soon after its discovery in 1985 , C60 received tremen- fullerenes’ high electron affinities, makes these materials dous attention due to its unique structure and properties. appealing for use in photoinduced electron transfer6） and 7） After several years of intensive research activity, C60 has also for applications in medicinal chemistry . Guldi and regarded as a molecule having tremendous potential as a Prato8） have recently reviewed the excited-state properties building block for molecular engineering, novel materials of C60 derivatives. synthesis, supramolecular chemistry, and also medicinal C60 has also demonstrated excellent capabilities in the chemistry2, 3）. The 20 hexagonal and 12 pentagonal rings quenching of various free radicals compared to conven- ＊Correspondence to: Lok Kumar Shrestha, World Premier International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044 JAPAN E-mail: [email protected] Accepted April 25, 2013 (received for review March 31, 2013) Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online http://www.jstage.jst.go.jp/browse/jos/ http://mc.manusriptcentral.com/jjocs 541 L. K. Shrestha, R. G. Shrestha, J. P. Hill et al. 9） 27, 28） tional antioxidants . Many fullerene-based compounds duction of tailored nanostructured crystalline C60 . Mi- have shown tremendous practical values biological yazawa and coworkers have developed a liquid-liquid inter- 10） systems although the highly hydrophobic character of C60 facial precipitation（LLIP）method for growing low （it is water insoluble）limits its application in biomaterials’ dimensional nanowhiskers or hollow tubular structures field. This problem has been addressed by many materials from solution under ambient conditions29, 30）. It should be chemists and water soluble fullerenes have been produced noted that if diameters of the 1D rod structure is in the by appropriate substitution or functionalization with ionic range of hundreds of nanometers to a few microns and and nonionic functional groups11）. Furthermore, amphiphil- lengths reach several hundreds of microns then they are ic fullerene derivatives have also been produced that can referred to as C60 nanowhiskers. In contrast to CNTs, C60 self-assemble into different mesostructures in solution or nanowhiskers do not contain any internal hollow spaces. 12） on a substrate . Water-soluble fullerene derivatives led to Rather, whiskers are composed of many C60 molecules the discovery of the interactions between organofullerenes bonded through a combination of van der Waals interac- and DNA, proteins, and living cells. C60 can also be encap- tions and chemical bonds. Miyazawa et al. have also ex- sulated in supramolecular structures containing a host tended this method to produce 2D hexagonal and polygo- moiety, such as cyclodextrin, surfactants, gels, or poly- nal shaped nanosheets31, 32）. Very recently, we extended mers13）. this method to produce giant microcrystals with macro- Needless to say significant advances in fullerene chemis- pores at their surfaces and also succeeded in fabricating, try have lead to a number of interesting developments in- for the first time, hexagonal-shaped crystalline fullerene cluding carbon nanotube（s CNTs）14）. This functional mole- with bimodal pore structures33, 34）. Furthermore, we utilized cule requires assembly into well-ordered one dimensional this method for the unusal formation of 3D highly crystal- （1D）or two dimenaiona（l 2D）forms to promote its elec- line cubic-shape crystals of C60-fullerene-Ag（I）organome- tronic and optical properties and to construct electronic or tallic heteronanostructure［C6｛0 AgNO3｝5］, which showed photonic devices15－17）. It is therefore essential to know the irreversible structural rearrangement upon gentle washing intermolecular ordering of C60 molecules at the micro and with aliphatic alcohols resulting in the formation of unique- macroscopic level for the production of dimension-con- ly structured formations of well-oriented C60 microcrys- 18） 35） trolled nanostructures of C60 . tals . In this review, we briefly summarize the recent develop- In solution-based crystal formation methods, the crystal ment of the production of low to higher dimensional nano- formation mechanism is suggested to be driven by super- structured fullerene（C60）crystals over different length saturation related to the low C60 solubility in alcohols scales and focussing on solution-based approaches and dif- （known as an antisolvent or a poor solvent for C60）. There- ferent self-assembled mesostructures of functionalized fore, the solubility of C60 is a key parameter for good and fullerenes. poor solvent selection. Rods or needles grow in arbitrary directions through the LLIP process at the interface of sat- urated C60 in toluene and isopropyl alcoho（l IPA）. In depth investigations on the production of structure controlled 2 NANOSTRUCTURED CRYSTALLINE FULLERENES crystalline fullerene have confirmed the fact that the mor- Nano-sized C60 crystals have received much attention phology and size of crystalline assembly of C60 largely and are considered to be intermediate states between mol- depend on the synthetic route, concentration of C60 in solu- ecules and bulk materials. Hierarchical assembly of C60 into tion, crystallization temperature, and mixing ratio of anti- nanocrystal（s or nanoparticles）offers unique properties solvent and solvent particularly in the precipitation with potential to be used in device fabrication. Bulky parti- method. Formation of 1D rods and 2D plate-like morpholo- cles without any unified shape of pristine C60 have the in- gies from slow evaporation of C60 solution and vapor depo- teresting property of forming crystalline assemblies of sition, respectively, can be taken as a good example. In the various well-defined morphologies and sizes depending on following section, we discuss recent advances for the lower the method of molecular assembly. Various synthetic ap- to higher dimensional nanostructured crystalline fullerene proaches have been explored to make 1D or 2D nanostruc- by solution-driven assembly methods. tures of C60. Templating, slow evaporation, and vapor-solid A very simple method
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