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Exohedral Functionalization of Endohedral Metallofullerenes

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Exohedral Functionalization of Endohedral Metallofullerenes Coordination Chemistry Reviews 388 (2019) 406–439 Contents lists available at ScienceDirect Coordination Chemistry Reviews journal homepage: www.elsevier.com/locate/ccr Review Exohedral functionalization of endohedral metallofullerenes: Interplay between inside and outside q ⇑ ⇑ Peng Jin a, , Ying Li a, Saneliswa Magagula b, Zhongfang Chen b, a School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China b Department of Chemistry, University of Puerto Rico, San Juan, PR 00931, USA article info abstract Article history: Endohedral metallofullerenes (EMFs) are fullerene cages enclosing various metallic species. The function- Received 26 December 2018 alization of EMFs has remarkably blossomed in recent years, in contrast to early efforts that were mainly Received in revised form 21 February 2019 devoted to their geometric and electronic structures as well as optical and magnetic properties. This Accepted 22 February 2019 review presents an exhaustive survey of the important functionalization approaches of EMFs, mainly Available online 21 March 2019 focusing on the progress since 2014. The involved reactions include silylation and germylation, Diels– In celebration of the 100th anniversary of Alder reaction, Bingel–Hirsch reaction, 1,3-dipolar cycloaddition, carbene addition, benzyne addition, free Nankai University. radical reaction, hydroxylation, dimerization, coordination reaction, noncovalent complexation, as well as numerous miscellaneous reactions. We summarize the main factors that affect the reactivity and Keywords: regioselectivity, focusing particularly on the intriguing interplay between the exohedral groups and inter- Fullerenes nal species. This work highlights the established role of current theoretical studies in further understand- Endohedral metallofullerenes ing the reactivity and regioselectivity of functionalization reactions. Finally, we discuss potential Chemical functionalization applications of exohedrally modified EMFs. Ó 2019 Elsevier B.V. All rights reserved. Contents Solid PDF Tools 1. Introduction ......................................................................................................... 407 2. Structures of typical EMFs . ......................................................................................... 407 3. Functionalization reactions . ......................................................................................... 410 3.1. Silylation and germylation . ............................................................................ 410 3.2. Diels–Alder cycloaddition . ............................................................................ 411 3.3. Prato reaction . ............................................................................................... 412 3.4. Bingel–Hirsch reaction . ............................................................................ 414 3.5. Carbene addition . ............................................................................................... 415 3.6. Benzyne cycloaddition . ............................................................................ 417 3.7. Radical reaction . ............................................................................................... 417 3.8. Polyhydroxylation ............................................................................................... 419 3.9. Dimerization reaction . ............................................................................ 420 3.10. Coordination reaction . ............................................................................ 422 3.11. Noncovalent modification. ............................................................................ 424 3.12. Miscellaneous reactions . ............................................................................ 425 4. Potential applications. ......................................................................................... 427 4.1. Photovoltaics . ............................................................................................... 427 4.2. Nanomaterials . ............................................................................................... 427 4.3. Biomedicine . ............................................................................................... 428 5. Concluding remarks . ......................................................................................... 429 http://www.SolidDocuments.com/ q This paper belongs to the special issue entitled ‘‘Coordination Chemistry goes multidisciplinary: The Centennial Celebration of Nankai University”. ⇑ Corresponding authors. E-mail addresses: [email protected] (P. Jin), [email protected] (Z. Chen). https://doi.org/10.1016/j.ccr.2019.02.028 0010-8545/Ó 2019 Elsevier B.V. All rights reserved. P. Jin et al. / Coordination Chemistry Reviews 388 (2019) 406–439 407 Acknowledgments . ................................................................................... 429 Appendix A. Supplementary data . ................................................................................... 429 References . ...................................................................................................... 429 1. Introduction recent years for several reasons: (1) it benefits the purification and separation of EMFs from fullerene mixtures; (2) it provides Endohedral metallofullerenes (EMFs), with metallic species an effective approach to stabilize the highly reactive small- (atoms or clusters) imprisoned in carbon cages, are novel metal– bandgap EMFs and make them obtainable; (3) the functionalized carbon hybrid molecules with interesting core–shell structures derivatives are easy to crystallize and can help structural charac- [1–6]. In the last three decades, the unique and tunable physico- terization of the parent EMFs by using X-ray crystallography; (4) chemical properties of EMFs have garnered research interest from external functional groups can be introduced, which can finely various fields such as photovoltaics, materials science and modulate the physical and chemical properties of EMFs to engen- biomedicine. der diversely applicable functional materials; (5) it assists in An EMF molecule is commonly denoted by M@C2n, where the increasing the solubility of EMFs by obtaining corresponding symbol @ indicates that the left metallic species are within the water-soluble derivatives that have potential applications in bio- right carbon cage [7]. EMFs all feature substantial charges (up to medicine; (6) the location, configuration and dynamic behavior 6e) donated by the enclosed metal atom/cluster to the fullerene of the internal metallic species can be effectively regulated for framework, and are thus commonly described by an ionic model the design of novel nanodevices and; (7) the relative position q+ qÀ M @C2n [8–11]. and orientation of fullerene molecules can be precisely controlled The mutual stabilization of the metal core and carbon shell via exohedral modification to achieve self-assembled nano systems endows EMFs a rather unique capability to encapsulate metal with well-ordered structures. In previous years, several excellent atoms/clusters into the fullerene cage and stabilize the otherwise review articles focusing on the functionalization of EMFs have been unstable carbon cages. Various reactive metallic species with a published [35–44]. Since the last dedicated contribution in 2014 maximum atom number of seven (Sc4O3 [12]) have been success- [42], however, significant strides have been made in this field, fully captured in EMFs due to the confinement effect and effective and a timely and comprehensive summary is thus highly desirable metal-cage interaction. Therefore, the interior space of fullerenes to guide the future development of EMFs functionalization. can serve as an ideal platform to study novel cluster structures. Herein, we present an exhaustive survey on the exohedral func- The stability of empty fullerenes is governed by the well-known tionalization of EMFs, mainly focusing on the new developments in isolated pentagon rule (IPR) [13], which states that each of the the last five years. Some early works missed in other reviews are twelve pentagons of a stable carbon cage should only have five also covered. The structure for the remainder of the paper is as fol- hexagons as near neighbors. However, the transfer of electrons lows: Section 2 introduces the molecular structures of representa- can efficiently convert an antiaromatic 8p-electron pentalene sub- tive EMFs. Section 3 summarizes all kinds of reported unit of a non-IPR fullerene cage to a local Hückel-aromatic 10p- functionalization reactions, including both experimental and theo- electron motif [14], thus the metal-to-cage charge transfer may retical progress. Section 4 briefly introduces the potential applica- partly alleviate the high strain and instability caused by fused pen- tions of the modified EMFs in different fields, followed by tagons. Encapsulation can therefore serve as an efficient approach Section 5—concluding remarks. to achieve non-IPR fullerenes [15]. Solid PDF Tools To date, more than two hundred EMF molecules have been 2. Structures of typical EMFs experimentally characterized. The interior metal mainly originates from Groups I to V on the periodic table and is dominated by Sc, Y For convenience, we first introduce the structures of EMFs fre- and lanthanides with the cages covering a wide size range. In the quently encountered in functionalization reactions. These include last two years, Th-
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