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Nanotechnology of Diamondoids for the Fabrication of Nanostructured Systems

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Nanotechnology of Diamondoids for the Fabrication of Nanostructured Systems Nanotechnology Reviews 2020; 9: 650–669 Review Ka-Wai Yeung, Yuqing Dong, Ling Chen, Chak-Yin Tang*, Wing-Cheung Law, and Gary Chi-Pong Tsui Nanotechnology of diamondoids for the fabrication of nanostructured systems https://doi.org/10.1515/ntrev-2020-0051 received June 15, 2020; accepted June 22, 2020 1 Introduction Abstract: Diamondoids are cage-like hydrocarbon materials Since the discovery of graphene, diamonds, and fullerenes, with unique characteristics such as low dielectric constants, hydrocarbon nanomaterials have come to the forefront of negative electron affinity,largestericbulk,andelectron- material science. Numerous research works on their basic donating ability. They are widely used for advanced func- properties and potential applications have been carried out tional materials in nanocomposite science. Surface modifica- [1–4]. Diamondoids, which were first discovered and tion of diamondoids also produces functional derivatives that extracted from crude oil by Landa and Machacek in 1933 broaden its applications. This article provides a concise [5],arecage-shaped hydrocarbon molecules that resemble a review of the fundamentals of diamondoids, including diamond lattice structure [6]. These naturally abundant their origin and functionalization, electronic structure, hydrocarbon materials inherit some of the superior properties optical properties, and vibrational characteristics. The of diamonds, such as excellent thermal stability with a high recent advances of diamondoids and their derivatives in melting point, high hardness, and stiffness, as well as applications, such as nanocomposites and thin film coat- excellent chemical resistance. Unlike the detonation nano- ings, are presented. The fabrication of diamondoid-based diamond [7],theyhaveawell-defined molecular structure, nanostructured devices, including electron emitters, catalyst with high purity and homogeneity in size distribution [8]. sensors, and light-emitting diodes, are also reviewed. Finally, Extensive studies on their physical properties have been thefuturedevelopmentsofthis unique class of hydrocarbon conducted. Selective chemical functionalization of dia- materials in producing a novel nanostructure system mondoid molecules has also been studied to broaden their using advanced nanotechnologies are discussed. This applications in the fields of organic and inorganic chemistry, review is intended to provide a basic understanding of materials science, and biomedical science [9].Applications diamondoid properties, discuss the recent progress of its such as pharmaceutical therapy, catalysis, polymer compo- modifications and functionalization, and highlight its sites, and optics have been developed [9–11]. novel applications and future prospects. Diamondoids and their derivatives have been used as 3 Keywords: diamondoids, sp hydrocarbon, nanocompo- functional additive materials and molecular building blocks sites, nanostructures in nanotechnology in a wide range of applications [12,13].For example, diamondoid–polymer nanocomposites with en- hanced thermal and mechanical stability have been produced [14].Flame-retarding polymer nanocomposites have been synthesized by using a widely used engineering plastic with surface modified diamondoids [15,16].Studieshavealso discovered that adding diamondoids into a polymer matrix [ ] * Corresponding author: Chak-Yin Tang, Department of Industrial may improve its transparency in the optical regime 17 , and Systems Engineering, The Hong Kong Polytechnic University, increase the refractive index with low optical dispersion [18], Hung Hom, Kowloon, Hong Kong, China, e-mail: cy.tang@polyu. and reduce the dielectric constant of the polymer [19].These edu.hk, tel: +852-2766-6608, fax: +852-2362-5267 unique features have made the diamondoid-containing - - - Ka Wai Yeung, Yuqing Dong, Wing Cheung Law, Gary Chi Pong Tsui: polymer nanocomposites suitable as optical and low-κ Department of Industrial and Systems Engineering, The Hong Kong dielectric materials. A variety of advanced applications of Polytechnic University, Hung Hom, Kowloon, Hong Kong, China - Ling Chen: Manufacturing BU, CSIRO, Private Bag 10, Clayton, diamondoid containing materials have been developed, South Vic 3169, Australia including electron emitters and catalyst sensors, due to the Open Access. © 2020 Ka-Wai Yeung et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0 Public License. Nanotechnology of diamondoids for the fabrication of nanostructured systems 651 Figure 1: Molecular structures of diamondoids. They can be classified as (1) lower diamondoids, which include adamantane, diamantane, and triamantane, and (2) higher diamondoids, e.g., tetramantane and pentamantane, with different isomeric structures. intrinsic properties of diamondoids such as negative infrared absorption spectrum of interstellar gas revealed the electron affinity, large steric bulk, and electron-donating potential existence of diamondoids in the interstellar medium ability [20,21].Thequantumconfinement and tunable [26–29]. These naturally abundant hydrocarbons have been band gap properties of diamondoid molecules [22,23] classified as a new class of diamond-like material that differs have also unleashed their potential in micro- and nano- from nanodiamonds, which are the mixtures of diamond electronic applications [24]. isomers. In the recent decades, they have attracted extensive In this review, the fundamentals and the functionaliza- research interest for their applications in polymer material tion of diamondoids are first briefly introduced. The physical upgrading and in optical and optoelectronic devices [9,11] properties of diamondoids, including optical properties, due to their diamond-like properties and superior stability electronic structure, vibration properties, and photolumi- compared to other carbon nanomaterials, as well as its nescence properties, are presented. Furthermore, this article unique functionality including low dielectric constant and also highlights the recent advances in diamondoids and photoluminescence [30]. their derivatives in various applications. We aim to provide a Balaban and Schleyers [31] have developed the naming comprehensive summary of the development of diamond- and classification of diamondoids based on the graph- oids containing material and state-of-the-art applications. theoretical approach. The general chemical formula of diamondoids is presented as C4n+6H4n+12. The smallest unit of the diamondoids group is named adamantane (C10H16), corresponding to the IUPAC naming of tricyclo[3.3.1.1(3.7)] 2 Fundamentals of diamondoids decane in the Baeyer systematic nomenclature [32].Itis followed by two polymantane homologs, namely, diaman- ( ) ( ) 2.1 Origin and nomenclature of tane C14H20 and triamantane C18H24 , which are also known as lower diamondoids and have only one isomer. For higher diamondoids diamondoids, different isomeric polymantanes can be distinguished using dualist graphs by joining the centers of The smallest unit of a diamondoid, adamantane, was first fused adamantane units in polymantane, and the numbers isolated from crude oil by fractional distillation in 1933 [5]. 1–4 are used to represent different orientations in the space of Later in 1966, diamantane, which contains two face-fused adamantane units. Figure 1 shows the molecular structures of adamantanes, was also discovered [25].Moreover,the diamondoids, which are also classified into lower and higher 652 Ka-Wai Yeung et al. diamondoids. Over the past few decades, adamantane has pharmacological activities [10,46]. Phosphine ligands been studied extensively due to its simple structure and ease bearing diamondoids have shown a good catalytic of functionalization with good selectivity [33]. It has been efficiency and broad reaction scope [47].Thisbulky used as a model structure to predict the properties of higher electron-rich diamondoid derivative has been applied in diamondoids [34]. palladium-catalyzed amination reactions for aryl chlor- Diamondoids can be prepared in a laboratory via ides at mild reaction conditions with an increased yield. chemical synthesis [35,36]. Lewis acid-catalyzed methods Thiol-functionalized diamondoids have been attached to have been well developed for diamondoids synthesis [8]. the surface of noble metals such as gold and silver via These methods allow the batch production of lower self-assembly [48,49]. Due to the negative electron affinity diamondoids in kilograms and higher diamondoids in of diamondoids, they can be potentially used as electron- multigram quantities, thereby facilitating the study of emission materials for electron beam lithography and these unique nanomaterials for advanced applications. electron microscopy applications. Other functionalization methods, including olefination and alkylation, have also been reported [50,51]. They are important for synthesizing novel diamondoids containing polymers via a copolymer- 2.2 Functionalization of diamondoids ization reaction. Apart from the direct functionalization of a single Diamondoids are cage-like hydrocarbon molecules with type of functional group, the substitutions of two or fully sp3 hybridized carbon and only secondary and more functional moieties, namely, unequal polyfunctio- tertiary sites on the surface [37]. Modifications of nalization of diamondoids, have also been developed diamondoids are necessary to extend their potential [9]. The functionalization and modification of diamond- applications. By replacing the hydrogen atoms on the oids provide
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