Recent Developments in the Synthesis of Inorganic Fluorides

Lutar, K.; Borrmann, Horst; Leblanc, M.

doi:10.1016/b978-044472002-3/50003-x

Cited by 8 publications

(7 citation statements)

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“…101 It is indeed strange that this has remained the only publication on this topic from the whole heptazine family. Also, very recently, Ratier, Trigaud, and Audebert demonstrated the possibility of using an electron deficient layer composed of a monomeric heptazine, TPDH (72), to enhance electron injection in deposited layers. Electron injection into an Alq3 layer was facilitated by a spin coated or thermally evaporated trispyrazolyl-s-heptazine interfacial layer and the electrode 119 which further demonstrated the emerging utility of this family of molecules in a diverse array of applications.…”

Section: Heptazines As Oled Materialsmentioning

confidence: 78%

“…All these syntheses require obviously a dedicated setup (just to avoid safety casualties). While industrial plants may envisage building a special facility or site/premises to perform this reaction safely on a medium size scale (after all, highly aggressive and toxic gases like, e.g., SF 5 , OF 2 , and NF 3 are used in some industrial processes 72 ), obviously relatively few fundamental research laboratories can make the choice to invest in such a heavy and delicate setup, especially if it also has to be adapted to the production of small or average quantities of trichloro-sheptazine.…”

Section: Introductionmentioning

confidence: 99%

“…Recent s-Heptazine Derivatives Prepared between 2012 and Today by SNAr Substitution of Trichloro-s-heptazine(8) or TDPH(72) h i b i t e d .…”

mentioning

confidence: 99%

“…Scheme 8. TDPH(72) along with Its Synthesis Starting from Tris(hydrazino)-s-heptazine, Which Can Be Directly Obtained from Melem or Melon and Aqueous Hydrazine 135 …”

mentioning

confidence: 99%

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State of the Art in the Preparation and Properties of Molecular Monomeric s-Heptazines: Syntheses, Characteristics, and Functional Applications

et al. 2021

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This review gives an account on the fast expanding field of monomeric (or molecular) heptazines, at the exclusion of their various polymeric forms, often referred to as carbon nitrides. While examples of monomeric heptazines were extremely limited until the beginning of this century, the field has started expanding quickly since then, as has the number of reports on polymeric materials, though previous reviews did not separate these fields. We provide here a detailed report on the synthetic procedures for molecular heptazines. We also extensively report on the different achievements realized from these new molecules, in the fields of physical chemistry, spectroscopy, materials preparation, (photo)catalysis, and devices. After a comprehensive summary and discussion on heptazines syntheses and characteristics, we show that starting from well-defined molecules allows a versatility of approaches and a wide tunability of the expected properties. It comes out that the field of monomeric heptazines is now emerging and possibly heading toward maturity, while diverging from the one of polymeric carbon nitrides. It is likely that this area of research will quickly surge to the forefront of the search for active organic molecules, with special attention to the domains of catalysis and organic-based functional materials and devices.

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Section: Heptazines As Oled Materialsmentioning

confidence: 78%

Section: Introductionmentioning

confidence: 99%

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State of the Art in the Preparation and Properties of Molecular Monomeric s-Heptazines: Syntheses, Characteristics, and Functional Applications

et al. 2021

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“…A comprehensive review on solid–solid, gas–solid, solution–solid reactions, eventually under low or high pressure, was published in 1985 by Grannec and Lozano . Two decades later, mild reaction conditions (related to “chimie douce”, despite the agressive nature of numerous involved fluorides) were prevailing, according to Lutar, Borrmann, and Leblanc . All of the mentioned techniques are still relevant today.…”

Section: Introductionmentioning

confidence: 99%

Crystal Chemistry and Selected Physical Properties of Inorganic Fluorides and Oxide-Fluorides

2014

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The stereochemistry of fluorides will be discussed in terms of dimensionality. This dimensionality, from 0D to 3D, is related to the connectivity of the building MX n m− units containing the metal M (M = aluminum, transition metal, or rare earth elements, X = F, O, N, S). These building units share eventually one, two, or three fluorine or oxygen atoms (corner, edge, or face of the MX n m− polyhedra) to form limited polyanions, infinite chains or layers, or a 3D network. Consequently, the structures will be presented according to their dimensionality, to their structural family, and to the nature of the building units. Imaginative associations of the building units will be eventually used to homogenize the structural descriptions. At the end of each section, some outstanding physical properties will be briefly presented and related to the structural data: ionic conductivity, superconductivity, ferroelasticity, and magnetism.The reader should be aware that the IUPAC nomenclature suggests "fluorido" instead of "fluoro" that is used all along this Review. All crystal structure projections were realized with Diamond software (Diamond -Crystal and Molecular Structure

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Fluorides: Solid‐State Chemistry

Massa

2005

Encyclopedia of Inorganic Chemistry

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Inorganic solid fluorides and fluorometalates play a unique role in inorganic chemistry. The preparation, mostly using aqueous or anhydrous HF or even elemental F 2 , requires special conditions: no glass or silicate containing vessels can be used. Their structural chemistry is governed by the outsider role of the fluoride anion. It is the smallest and least polarizable anion and its mainly ionic compounds follow the rules of hard spheres packing better than any other class of substances. Nearly all metal ions except those with the largest ionic radii form fluoride structures with octahedral [M n + F 6 ] (6− n )– units. If the metal:fluorine ratio is less than 6, these octahedra share common vertices or, in rare cases, edges or even faces to account for electroneutrality, the more the lower the oxidation state of the metal. In this way, a variety of 1D chain, 2D net, and 3D framework structures is formed that can be classified into a few large structure families. In binary fluorides, for example, VF 5 has an octahedral cis‐chain structure, VF 4 a layer structure based on a square net of corner‐connected octahedra, VF 3 has a ReO 3 ‐related 3D structure with all corners of octahedra connected, and VF 2 has the rutile‐type structure with partial edge‐sharing of octahedra. In ternary or quaternary compounds, for example, alkali or alkaline earth fluorometalates, the same principles are valid for the anionic substructure while the counter cations fill interstices and stabilize at the same time the structure. The main structure families are grouped according to the basic principles of octahedral nets. These are the ReO 3 ‐related trifluorides, the fluoride perovskites AMF 3 , their relatives elpasolites A 2 A′MF 6 , and cryolites A 3 MF 6 , as well as some layer structures with square nets. A second large family is based on mixed octahedral nets including triple units: it includes for example, the pyrochlores, the weberites, the hexagonal and tetragonal tungsten bronze structures, and some derivable layer structures. Recent developments deal with ‘tailoring’ of low‐dimensional or framework structures using ‘soft‐chemistry’ methods. The relatively simple structural chemistry of fluorides invoked their use as model systems, for instance, for the investigation of electronic effects like Jahn–Teller ordering, or for magnetic investigations. Besides the cryolite Na 3 AlF 6 used in Al production, some fluorides are of technical interest owing to their special optical properties (e.g. laser optics, fluoride glasses), their ability for fluoride ion conductivity, or their role as catalysts for fluorinations or halogene exchange in organic systems.

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Recent Developments in the Synthesis of Inorganic Fluorides

Cited by 8 publications

References 261 publications

State of the Art in the Preparation and Properties of Molecular Monomeric s-Heptazines: Syntheses, Characteristics, and Functional Applications

State of the Art in the Preparation and Properties of Molecular Monomeric s-Heptazines: Syntheses, Characteristics, and Functional Applications

Crystal Chemistry and Selected Physical Properties of Inorganic Fluorides and Oxide-Fluorides

Fluorides: Solid‐State Chemistry

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