The series Structure and Bonding publishes critical reviews on topics of research concerned with 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. Readership: research scientists at universities or in industry, graduate students.

Materials synthesis is a field at the intersections of chemistry and physics with wide-ranging applications. There is a rich diversity of techniques to develop novel materials, but very little fundamental understanding of the mechanisms that drive the formation of solids, leading to an inability to predict a synthesis for a material with targeted properties. Solvothermal synthesis has garnered much attention in the field due to its relative predictability by combining solution-phase dynamics with reactive inorganic precursors. By incorporating composition-guided organic chemistry, which often benefits from predictable properties, metal-organic frameworks (MOFs) synthesized solvothermally have emerged among the most rationally designed solids in modern science. MOFs are a class of crystalline materials composed of metal-centers linked by organic ligands, forming large, porous networks. Structures, thus some properties, can be predicted given motifs for previously determined metal-center geometries and ligand-bonding environs. Further, targeted properties can be chemically tuned via optimization of the ligand and/or metal. Early efforts in the field resulted in the intriguing materials that failed to be commercially viable due to stability issue. Metal-organic frameworks using lanthanide metal-centers (Ln-MOFs) are thought to increase thermodynamic stability of the material and present unique electronic properties such as photoluminescence. The projects presented herein focus on investigating the properties and stability of lanthanide metal-organic frameworks with a naphthalene-based ligand. To be a commercially viable material, among other things a MOF must be stable in addition to having practical properties. The increased complexity in both the accessible geometries and electronic properties of lanthanides relative to light transition metals makes this work largely exploratory. Novel, isostructural cerium, neodymium, and europium Ln-MOFs comprised of two-dimensional sheets of metal-carboxylate centers bridged by naphthalene were synthesized and photoluminescence properties analyzed. The series of Ln-MOFs studied show they have robust photoactivity that may be exploited in small molecule or ion sensing. Compound [Ce(NO3)(NDC)][sub n] was found to be stable under basic and acidic aqueous conditions, but not thermally stable to 400°C. Small aromatic molecules were screened against [Nd(NO3)(NDC)][sub n] and fluorescence quenching shown to be correlated to spectral overlap, with significant signal quenching of benzene, but no observed selective change in excitation or emission wavelengths. Further, the compound was found to be stable to 300°C in open air. In particular, compound [Eu(NO3)(NDC)][sub n] was shown to be highly fluorescent in water and is readily quenched by trace concentrations of hazardous industrial by-product chromic acid. These investigations represent a broad effort to characterize Ln-MOFs in hopes of guiding the development of similar materials that exhibit robust chemical and thermal stability and relevant properties. Isoreticular synthesis is generally, but not exactly, an appropriate tool for replicating the synthesis with naphthalene-based ligands but different lanthanide metals. Procedurally altering the reported successful synthetic conditions with lanthanide metals is highly likely to produce isostructural and comparably stable compounds that exhibit unique electronic properties. Solvothermal synthesis using thiourea as a reactive solvent was also shown to produce unique lanthanide-metalloid complex germanium (II) sulfide doped lanthanum (III) hydroxide. The complex was found to photocatalytically degrade dye methylene blue in water under UV irradiation. While, not as efficient as known photocatalyst anatase titania, it represents a new class of lanthanum oxides doped with small band gap semiconductors that may be more easily optimized for photocatalytic processes than investigations on titanium dioxide have proven to be. Such intercalated lanthanum oxides may even have other relevant photo-driven applications, such as light harvesting or water-splitting.

Metal Organic Frameworks: Fundamentals to Advanced offers a substantial and complete treatment of published results. The book includes a summary of current research, along with an in- depth explanation of Metal organic frameworks (MOFs) and applications in this versatile area. Metal organic frameworks (MOFs) are structured frameworks made up of metal ions and organic molecules. These materials are similar to sponges and can absorb, retain and remove molecules from their pores. As a result, metal-organic frameworks (MOFs) are the most rapidly evolving substances in chemistry with the highest surface areas due to their well-ordered pore structure.The exciting and vast surface area allows for more chemical reactions and molecule adsorption, hence this new resource provides the newest updates on the topics covered. - Covers the synthetic advantages and versatile applications of metal-organic frameworks (MOFs) due to their organic-inorganic hybrid nature and unique porous structure - Includes energy applications such as batteries, fuel storage, fuel cells, hydrogen evaluation reactions and super capacitors - Features information on using MOFs as a replacement to conventional engineering materials as they are lightweight, less costly, environmentally-friendly and sustainable

Synthesis of Metal-Organic Frameworks via Water-Based Routes: A Green and Sustainable Approach describes a sustainable approach for the synthesis of metal-organic frameworks. Bringing together chapters on the aqueous synthesis and stability of metal-organic frameworks, as well as the applications of water stable metal-organic frameworks, this timely book shows how green processing technology utilizing water as a main solvent for the synthesis of metal-organic frameworks can eliminate solvent consumption, lower investment costs and reduce energy requirements. Providing quantitative descriptions and reliable guidelines, the book summarizes the fundamental approaches and principles to prepare metal-organic frame works, highlighting the most exciting preparations and applications. - Includes the role of water in metal organic synthesis - Describes various methods of metal-organic framework preparation - Covers the industrial aspects of water-based metal-organic frameworks and potential applications

This thesis provides essential information on the systematic design of assembled lanthanide complexes for functional luminescent materials. It discusses the relationships between assembled structures and photo, thermal, and mechanical properties on the basis of crystallography, spectroscopy, and thermodynamics. The described guidelines for assembled structures will be extremely valuable, both for industrial applications and for readers’ fundamental understanding of solid-state photophysics and materials chemistry. Luminescent lanthanide complexes are promising candidates for lighting devices, lasers, and bio-probes owing to their line-like and long-lived emission arising from characteristic 4f–4f transitions. Low-vibrational and asymmetrical coordination structures around lanthanide ions have been introduced to achieve strong luminescence, using specific organic ligands. Recently, assembled lanthanide complexes including coordination polymers and metal organic frameworks have increasingly attracted attention as a new class of luminescent materials offering thermal stability and color tunability. However, improving the luminescence efficiencies of these compounds remains a challenge, and specific molecular designs to control assembled structures and yield additional physical properties have not been established. The author provides a group of bent-angled bridging ligands to boost photoluminescence efficiency, and successfully introduces for the first time glass formability and strong triboluminescence properties.

The series Structure and Bonding publishes critical reviews on topics of research concerned with 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. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.

Unique properties of luminescent lanthanides reporters explain their emergence for bioanalytical and optical imaging applications. Lanthanide ions possess long emission lifetimes, a good resistance to photodecomposition and sharp emission bands that do not overlap. In addition, several lanthanides emit in the near infrared (NIR) region of the electromagnetic spectrum making them very interesting for in vivo imaging. Free lanthanide cations have low extinction coefficients due to the forbidden nature of the f → f transition. Therefore, lanthanides must be sensitized using a photonic converter such as an organic chromophore through the “antenna effect". We report here new near-infrared emitting compounds whose structure allows to incorporate a high density of lanthanide cations and sensitizers per unit volume: i) nano-MOF Yb-PVDC-3 based on Yb3+ sensitized by phenylenevinylene dicarboxylates. ii) polymetallic dendrimer complexes formed with derivatives of new generation-3 polyamidoamine dendrimers. In these complexes, 8 lanthanide ions (Eu3+, Yb3+, Nd3+) can be sensitized by the 32 antenna derived from 1,8-naphthalimide. These two families of compounds were fully characterised for their physical, photophysical properties as well as for their biological respective compatibilities. They are stable in various media and their low cytotoxicity and emission of a sufficient number of photons are suitable for near-infrared live cell imaging. One of the main goal outcomes of this work is the establishment of the proof of principle that nano- MOFs and lanthanide derived dendrimers can be used for the sensitization of NIR emitting lanthanides to create a new generation of NIR optical imaging agents suitable for both in cellulo and in vivoapplications.The present work also validates the efficiency of the strategy to use both types of nanoscale systems described here to increase the number of emitted photons per unit volume for an improved detection sensitivity and to compensate for low quantum yields.

The emerging and interesting field of MOF encouraged us to bring forth the book titled ''Metal Organic Frameworks''. The book is divided into three sections. Section A consists of introduction, Section B comprises the synthesis and characterization techniques, and Section C is dedicated to the applications of MOFs. The book would be useful for scientists and researchers interested in the field of MOFs.