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Chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant.

The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed.

Review articles for the individual volumes are invited by the volume editors



Layered Double Hydroxide Materials: Assembly and Photofunctionality

As a large type of inorganic layered compounds with diversity of composition in host layer and interlayer anions, layered double hydroxides (LDHs) have been intensively studied toward construction of advanced photofunctional materials. In this chapter, the optical properties of LDH materials and related potential applications—mainly involving the functionalities of LDH layers (such as tunable color, infrared radiation (IR) absorption, and ultraviolet (UV) shielding)—will be described firstly. Then, we will review the development of intercalated luminescent materials by adjusting both the host layer and guest molecules, in which the static and dynamic photofunctional modulations have been focused. Due to the host–guest and guest–guest interaction, fluorescence properties of composites can be effectively altered, and intelligent materials with stimuli-responsive performance can be further obtained. Finally, perspectives on the future development of LDH-based solid-state luminescent materials are addressed.
Rui Tian, Dongpeng Yan, Min Wei

Layered Rare Earth Hydroxides: Structural Aspects and Photoluminescence Properties

Layered rare earth hydroxides (LREHs), a special class of layered solids featuring cationic host layers of rare earth (RE) hydroxides, have become recognized as novel multifunctional materials in which the intercalation reactivity and host–guest interaction are coupled with the appealing physicochemical properties of RE elements. This chapter presents a background survey and an up-to-date overview on the development of LREH materials in terms of their synthesis, structural characterization, and photoluminescence properties. We first summarize the synthetic strategies to produce LREHs in various forms. In the following section, the basic structural features of LREH compounds are illustrated for typical anionic forms, and we highlight the critical importance of this knowledge in interpreting their fundamental properties and functionality hunting. Then, the photoluminescence properties of LREH compounds are discussed. Various phosphors with tunable or enhanced performance, including forms of oriented films, exfoliated nanosheet crystallites, and hybrid nanocomposites, are designed based on the structural features of LREH compounds. We describe the major contributions to this topic from studies conducted before 2015.
Jianbo Liang, Renzhi Ma, Takayoshi Sasaki

Layered Double Hydroxide Materials in Photocatalysis

Layered double hydroxide (LDH)-based photocatalysts have attracted great attention in the fields of environment and energy (e.g., degradation of pollutants, water splitting for solar fuel production), owing to their unique intercalation structure with highly dispersed metal cations and exchangeable anions, large specific surface areas, and remarkable adsorption capacities. This chapter aims to review and summarize the recent advances in the synthesis and photocatalytic applications of LDH-based materials. Typically, several important strategies have been developed for the fabrication of LDH-based photocatalysts by tuning the composition of the host layers, intercalating guest sensitizers, and constructing nanocomposites. The obtained photocatalysts exhibit excellent performances in the fields of pollutant degradation, water splitting, and reduction of CO2 into carbon sources. The fabrication and application of LDH-based photocatalysts represent a promising direction in the development of LDH-based multifunctional materials, which will contribute to the progress of chemistry and material science.
Mingfei Shao, Min Wei, David G. Evans, Xue Duan

Bio-Layered Double Hydroxides Nanohybrids for Theranostics Applications

Bio-related science has been one of the most important fields in the viewpoint of health and welfare of human being. A biofunctionalization of inorganic nanoparticles becomes more and more important in the near future, since it allows what is called theranostics, a new concept of next-generation medicine that combines therapeutics and diagnosis. Ever since the notion of intercalative bioinorganic nanohybrids was created based on the layered double hydroxide (LDH) material, a variety of bio-LDH nanohybrids have been developed to provide new opportunities toward theranostic biomedical applications. In this chapter, we review the structural chemistry of several bio-LDH nanohybrids available for gene and drug delivery system and focus on the platform strategies for advanced theranostic system. The cellular trafficking mechanism of LDH and cancer therapeutic efficacy along with diagnostic imaging of the bio-LDH nanohybrids are also discussed in in vitro as well as in vivo studies.
Dae-Hwan Park, Goeun Choi, Jin-Ho Choy

Photochromic Intercalation Compounds

Photochromism of intercalation compounds has been investigated so far. Starting from fundamental studies on the photochromic reactions of the dyes in the presence of layered materials, the precise design of the nanostructures of intercalation compounds toward controlled photochemical reactions and the creation of novel photoresponsive supramolecular systems based on layered solids have been a topic of interests. Various layered materials with different surface chemistries have been used as hosts for the controlled orientation, and aggregation of the intercalated dyes and the states of the intercalated guests affected photoresponses. Molecular design of the photochromic dyes has also been conducted in order to organize them on layered solids with the desired manner. On the other hand, layered solids with such functions as semiconducting and magnetic have been examined to host photochromic dyes for the photoresponsive changes in the materials’ properties.
Tomohiko Okada, Minoru Sohmiya, Makoto Ogawa

Photochemistry of Graphene

As a two-dimensional (2D) giant polycyclic aromatic molecule, graphene provides a great opportunity for studying the behaviors of chemical reactions in two dimensions. However, the chemistry of graphene is challenging because of its extreme inertness due to the highly delocalized π electron system. Recently, photogenerated free radicals have been demonstrated to effectively activate the chemical reactions of graphene. Such kinds of graphene photochemistry provide a new route for the covalent functionalization and band structure engineering of zero-gap graphene. In this chapter, the graphene photochemistry based on photogenerated free radicals is reviewed, including photohalogenation, photoarylation, photoalkylation, and photocatalytic oxidation. Although most photochemical reactions on graphene can be inspired by its small organic analogues, graphene photochemistry is of particular attraction due to its infinite 2D geometry, which offers a platform for studying geometry-correlated covalent chemistry, including single- and double-sided covalent addition reactions, asymmetric chemistry on two faces of monolayer graphene, edge-selective chemistry, and interlayer coupling-dependent few-layer graphene chemistry. In addition to the modulation of surface properties and the band structure engineering, new 2D derivatives and superlattices with fascinating features beyond mother graphene can be built by graphene photochemistry, which greatly expands the graphene family and its attraction. This chapter also summarizes the potential applications of graphene photochemistry with a specific focus being laid on the general consideration and understanding of graphene photochemistry towards electronic/optoelectronic devices and materials science. At the end, a brief discussion on the future directions, challenges, and opportunities in this emerging area is provided.
Liming Zhang, Zhongfan Liu


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