Solutions of alkali metals in anhydrous pyridine

Schmulbach, C. D.; Hinckley, C.C.; Wasmund, David

doi:10.1021/ja01026a006

Cited by 55 publications

(24 citation statements)

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“…Previously, there have been reports of metal atoms of Na, Li or Cs when dissolved in pyridine gave yellow solution with ESR activity in frozen state due to the formation of pyridine radical anion which rapidly reacted at room temperature to form 4,4 0 -bipyridyl radical anion. 45 The PVP-IL system, in our observation was similar to this provided that the electron supplying agent was a polymer, not a metal. The relatively comparable energy levels of PVP and bpy[BF 4 ] would have favoured an effortless electron migration from PVP to pyridinium moiety.…”

Section: Resultssupporting

confidence: 67%

Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe₂O₃doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

et al. 2017

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Section: Resultssupporting

confidence: 67%

Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe₂O₃doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

et al. 2017

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“…Ammonia or short-chain primary amines are considered as small molecules with lower enthalpies of solvation and are favored to form concentrated solutions of alkali metals. A similar behavior was found also in diamines (Zurek, 2011 ) and aromatic pyridine (Schmulbach et al, 1968 ). On the search for other molecules that may be intercalated between the layers of iron selenide, it was confirmed that the insertion of other donors such as LiFeO 2 or [(Li 1− x Fe x )OH] is also possible, resulting in T c = 40 K, though accompanied by a ferromagnetic contribution visible in a low-temperature region (Lu et al, 2014 ; Pachmayr et al, 2015 ; Sun et al, 2015 ).…”

Section: Intercalated Iron Selenide—the Influence Of the Chemical And Electrochemical Nature Of Intercalating Species On The Crystal Strusupporting

confidence: 76%

Intercalated Iron Chalcogenides: Phase Separation Phenomena and Superconducting Properties

Krztoń‐Maziopa

2021

Front. Chem.

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Organic molecule-intercalated layered iron-based monochalcogenides are presently the subject of intense research studies due to the linkage of their fascinating magnetic and superconducting properties to the chemical nature of guests present in the structure. Iron chalcogenides have the ability to host various organic species (i.e., solvates of alkali metals and the selected Lewis bases or long-chain alkylammonium cations) between the weakly bound inorganic layers, which opens up the possibility for fine tuning the magnetic and electrical properties of the intercalated phases by controlling both the doping level and the type/shape and orientation of the organic molecules. In recent years, significant progress has been made in the field of intercalation chemistry, expanding the gallery of intercalated superconductors with new hybrid inorganic–organic phases characterized by transition temperatures to a superconducting state as high as 46 K. A typical synthetic approach involves the low-temperature intercalation of layered precursors in the presence of liquid amines, and other methods, such as electrochemical intercalation, intercalant or ion exchange, and direct solvothermal growths from anhydrous amine-based media, are also being developed. Large organic guests, while entering a layered structure on intercalation, push off the inorganic slabs and modify the geometry of their internal building blocks (edge-sharing iron chalcogenide tetrahedrons) through chemical pressure. The chemical nature and orientation of organic molecules between the inorganic layers play an important role in structural modification and may serve as a tool for the alteration of the superconducting properties. A variety of donor species well-matched with the selected alkali metals enables the adjustment of electron doping in a host structure offering a broad range of new materials with tunable electric and magnetic properties. In this review, the main aspects of intercalation chemistry are discussed, involving the influence of the chemical and electrochemical nature of intercalating species on the crystal structure and critical issues related to the superconducting properties of the hybrid inorganic–organic phases. Mutual relations between the host and organic guests lead to a specific ordering of molecular species between the host layers, and their effect on the electronic structure of the host will be also argued. A brief description of a critical assessment of the association of the most effective chemical and electrochemical methods, which lead to the preparation of nanosized/microsized powders and single crystals of molecularly intercalated phases, with the ease of preparation of phase pure materials, crystal sizes, and the morphology of final products is given together with a discussion of the stability of the intercalated materials connected with the volatility of organic solvents and a possible degradation of host materials.

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“…This assumption is supported by similar observations made in solutions in pyridine, which have been prepared via dissolution in ammonia followed by addition of pyridine and slow evaporation of the ammonia. In such solutions at ambient temperatures decomposition reactions take place indicated by the color change resulting from the well‐known formation of the bipyridinyl radical . This reaction can be avoided by keeping the temperature permanently below –20 °C, and with this condition compounds including undecomposed Si 9 cluster are accessible, e.g.…”

Section: Discussionmentioning

confidence: 99%

Silicon Containing Nine Atom Clusters from Liquid Ammonia Solution: Crystal Structures of the First Protonated Clusters [HSi₉]^3– and [H₂{Si/Ge}₉]^2–

Henneberger

Klein

Fässler

2018

Zeitschrift anorg allge chemie

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Solutions of alkali metals in anhydrous pyridine

Cited by 55 publications

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Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe₂O₃doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe₂O₃doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

Intercalated Iron Chalcogenides: Phase Separation Phenomena and Superconducting Properties

Silicon Containing Nine Atom Clusters from Liquid Ammonia Solution: Crystal Structures of the First Protonated Clusters [HSi₉]^3– and [H₂{Si/Ge}₉]^2–

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Solutions of alkali metals in anhydrous pyridine

Cited by 55 publications

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Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe2O3doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe2O3doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

Intercalated Iron Chalcogenides: Phase Separation Phenomena and Superconducting Properties

Silicon Containing Nine Atom Clusters from Liquid Ammonia Solution: Crystal Structures of the First Protonated Clusters [HSi9]3– and [H2{Si/Ge}9]2–

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Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe₂O₃doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

Synthesis, characterization and theoretical studies on novel organic–inorganic hybrid ion–gel polymer thin films from a γ-Fe₂O₃doped polyvinylpyrrolidone–N-butylpyridinium tetrafluoroborate composite via intramolecular thermal polymerization

Silicon Containing Nine Atom Clusters from Liquid Ammonia Solution: Crystal Structures of the First Protonated Clusters [HSi₉]^3– and [H₂{Si/Ge}₉]^2–