Mechanochemistry: opportunities for new and cleaner synthesis
TL;DR: Concentrating on recent advances, this article covers industrial aspects, inorganic materials, organic synthesis, cocrystallisation, pharmaceutical aspects, metal complexes, supramolecular aspects and characterization methods.
Abstract: The aim of this critical review is to provide a broad but digestible overview of mechanochemical synthesis, i.e. reactions conducted by grinding solid reactants together with no or minimal solvent. Although mechanochemistry has historically been a sideline approach to synthesis it may soon move into the mainstream because it is increasingly apparent that it can be practical, and even advantageous, and because of the opportunities it provides for developing more sustainable methods. Concentrating on recent advances, this article covers industrial aspects, inorganic materials, organic synthesis, cocrystallisation, pharmaceutical aspects, metal complexes (including metal–organic frameworks), supramolecular aspects and characterization methods. The historical development, mechanistic aspects, limitations and opportunities are also discussed (314 references).
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TL;DR: The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.
Abstract: The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.
2,582 citations
TL;DR: In this paper, the chemical, thermal and mechanical stabilities of MOFs, in particular with catalytic uses in mind, are discussed, and future directions of study for the production of highly stable MOFs are briefly discussed.
Abstract: The construction of thousands of well-defined, porous, metal–organic framework (MOF) structures, spanning a broad range of topologies and an even broader range of pore sizes and chemical functionalities, has fuelled the exploration of many applications. Accompanying this applied focus has been a recognition of the need to engender MOFs with mechanical, thermal and/or chemical stability. Chemical stability in acidic, basic and neutral aqueous solutions is important. Advances over recent years have made it possible to design MOFs that possess different combinations of mechanical, thermal and chemical stability. Here, we review these advances and the associated design principles and synthesis strategies. We focus on how these advances may render MOFs effective as heterogeneous catalysts, both in chemically harsh condensed phases and in thermally challenging conditions relevant to gas-phase reactions. Finally, we briefly discuss future directions of study for the production of highly stable MOFs. Metal–organic frameworks (MOFs) have shown promise in a broad range of applications, including catalysis. In this Review, the chemical, thermal and mechanical stabilities of MOFs, in particular with catalytic uses in mind, are discussed.
1,332 citations
TL;DR: This Review considers several aspects of the most prominent sustainable organicsolvents in use today, ionic liquids, deep eutectic solvents, supercritical fluids, switchable solVents, liquid polymers, and renewable solvent, giving a more complete picture of the current status of sustainable solvent research and development.
Abstract: Sustainable solvents are a topic of growing interest in both the research community and the chemical industry due to a growing awareness of the impact of solvents on pollution, energy usage, and contributions to air quality and climate change. Solvent losses represent a major portion of organic pollution, and solvent removal represents a large proportion of process energy consumption. To counter these issues, a range of greener or more sustainable solvents have been proposed and developed over the past three decades. Much of the focus has been on the environmental credentials of the solvent itself, although how a substance is deployed is as important to sustainability as what it is made from. In this Review, we consider several aspects of the most prominent sustainable organic solvents in use today, ionic liquids, deep eutectic solvents, supercritical fluids, switchable solvents, liquid polymers, and renewable solvents. We examine not only the performance of each class of solvent within the context of the...
1,051 citations
Slovak Academy of Sciences1, Comenius University in Bratislava2, Bulgarian Academy of Sciences3, Spanish National Research Council4, University of Cagliari5, University of Lorraine6, Council of Scientific and Industrial Research7, Jožef Stefan Institute8, Keio University9, Moscow Institute of Physics and Technology10, Russian Academy of Sciences11
TL;DR: The aim of this review article is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemistry.
Abstract: The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).
908 citations
23 May 2016
TL;DR: A review of general purpose solvent selection guides can be found in this paper, highlighting their similarities and differences and how they can be used to enhance the greenness of chemical processes, particularly in laboratory organic synthesis and the pharmaceutical industry.
Abstract: Driven by legislation and evolving attitudes towards environmental issues, establishing green solvents for extractions, separations, formulations and reaction chemistry has become an increasingly important area of research Several general purpose solvent selection guides have now been published with the aim to reduce use of the most hazardous solvents This review serves the purpose of explaining the role of these guides, highlighting their similarities and differences How they can be used most effectively to enhance the greenness of chemical processes, particularly in laboratory organic synthesis and the pharmaceutical industry, is addressed in detail
756 citations
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TL;DR: In this paper, a structure refinement method was described which does not use integrated neutron powder intensities, single or overlapping, but employs directly the profile intensities obtained from step-scanning measurements of the powder diagram.
Abstract: A structure refinement method is described which does not use integrated neutron powder intensities, single or overlapping, but employs directly the profile intensities obtained from step-scanning measurements of the powder diagram. Nuclear as well as magnetic structures can be refined, the latter only when their magnetic unit cell is equal to, or a multiple of, the nuclear cell. The least-squares refinement procedure allows, with a simple code, the introduction of linear or quadratic constraints between the parameters.
14,360 citations
TL;DR: In this paper, a highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield.
Abstract: Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.
5,061 citations
TL;DR: Transition-Metal-Free Reactions, Alkynylation of Heterocycles, and Synthesis of Electronic and Electrooptical Molecules: A Review.
Abstract: 3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906
2,522 citations
2,308 citations
TL;DR: A set of general guidelines for structure refinement using the Rietveld (whole profile) method has been formulated by the International Union of Crystallography Commission on Powder Diffraction.
Abstract: A set of general guidelines for structure refinement using the Rietveld (whole-profile) method has been formulated by the International Union of Crystallography Commission on Powder Diffraction. The practical rather than the theoretical aspects of each step in a typical Rietveld refinement are discussed with a view to guiding newcomers in the field. The focus is on X-ray powder diffraction data collected on a laboratory instrument, but features specific to data from neutron (both constant-wavelength and time-of-flight) and synchrotron radiation sources are also addressed. The topics covered include (i) data collection, (ii) background contribution, (iii) peak-shape function, (iv) refinement of profile parameters, (v) Fourier analysis with powder diffraction data, (vi) refinement of structural parameters, (vii) use of geometric restraints, (viii) calculation of e.s.d.'s, (ix) interpretation of R values and (x) some common problems and possible solutions.
1,808 citations