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Chalcogen-Nitrogen Chemistry
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Chalcogen-Nitrogen Chemistry

A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (31 July 2013) | Viewed by 27704

Special Issue Editor

Prof. Dr. J. Derek Woollins

E-Mail Website
Guest Editor
Department of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
Interests: synthesis; p block chemistry; phosphorus; sulphur; selenium; tellurium; structural science; molecular main group chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Sulfur-nitrogen heterocycles (and Se-N/Te-N systems) have been known for many years but continue to excite attention as a consequence of the exciting new systems which are being prepared sometimes by rather unpredictable routes. Apart from fundamental synthetic and mechanistic chemistry new S-N, organo S-N (and their heavier selenium and tellurium congeners) have great potential in new electronic and magnetic materials. The area encompasses synthesis, heterocycles, ionic materials, conductors, superconductors, new magnetic materials and utilises a wide range of computational and spectroscopic methods.

Prof. Dr. Derek Woollins
Guest Editor

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Keywords

  • sulfur-nitrogen
  • selenium-nitrogen
  • thiazyl
  • selenazole
  • tellurazole
  • heterocycle
  • ring
  • materials
  • synthesis
  • structure
  • magnetism
  • organo-sulfur-nitrogen
  • organo-seleno-nitrogen

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Published Papers (3 papers)

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Research

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20 pages, 1433 KiB  
Article
A Variable Temperature X-ray Diffraction Investigation of [PPN+][S4N5−]: Supramolecular Interactions Governing an Order/Disorder Transformation and the First High Resolution X-ray Structure of the Anion
by René T. Boeré, Tracey L. Roemmele and Maria K. Krall
Molecules 2014, 19(2), 1956-1975; https://doi.org/10.3390/molecules19021956 - 12 Feb 2014
Cited by 6 | Viewed by 7638
Abstract
The title salt, triphenyl(P,P,P-triphenylphosphineimidato-kN)-phosphorus(1+) 1,3,5,7-tetrathia(1,5-SIV)-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1,4,6,7-tetraene(1−), CAS [48236-06-2], prepared by the literature method, is found by crystallography to be a 1:1 CH3CN solvate. Disorder exists for the N atoms of the anion. A VT crystal [...] Read more.
The title salt, triphenyl(P,P,P-triphenylphosphineimidato-kN)-phosphorus(1+) 1,3,5,7-tetrathia(1,5-SIV)-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1,4,6,7-tetraene(1−), CAS [48236-06-2], prepared by the literature method, is found by crystallography to be a 1:1 CH3CN solvate. Disorder exists for the N atoms of the anion. A VT crystal structure study was conducted at 100 K, 120 K, 140 K, 172 K, 200 K, 240 K and 280 K. The 100 K structure is superior, with only 10% of a second anion position oppositely-oriented w.r.t the diad axis of point group 2mm. At 120 K, an adjacent two-site disorder is encountered, but at higher temperatures three-site disorder with both opposite and adjacent placements of S4N5− ions is required w.r.t. the primary component. At 240 and especially 280 K, the anion nitrogen atoms appear fully scrambled amongst the six possible sites on the edges of an S4 tetrahedron with 83.3% occupancy for each. The PPN+ geometry does not show strong cation-cation interactions. However, there are numerous supramolecular contacts corresponding mostly to non-classical H-bonds between PPN+ ions and S4N5− as well as CH3CN. The geometry of the anion is corroborated from B3LYP/6-311++G(3df) DFT calculations, and the infra-red spectrum was assigned with excellent agreement between experimental and calculated frequencies. Full article
(This article belongs to the Special Issue Chalcogen-Nitrogen Chemistry)
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Review

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32 pages, 1299 KiB  
Review
Transition Metal Complexes and Radical Anion Salts of 1,10-Phenanthroline Derivatives Annulated with a 1,2,5-Tiadiazole and 1,2,5-Tiadiazole 1,1-Dioxide Moiety: Multidimensional Crystal Structures and Various Magnetic Properties
by Yoshiaki Shuku and Kunio Awaga
Molecules 2014, 19(1), 609-640; https://doi.org/10.3390/molecules19010609 - 7 Jan 2014
Cited by 7 | Viewed by 9595
Abstract
Advances in the molecular variety and the elucidation of the physical properties of 1,10-phenanthroline annulated with 1,2,5-thiadiazole and 1,2,5-thiadiazole 1,1-dioxide moieties have been achieved, and are described herein. A 1,2,5-thiadiazole compound, [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (tdap), was used as a ligand to create multidimensional [...] Read more.
Advances in the molecular variety and the elucidation of the physical properties of 1,10-phenanthroline annulated with 1,2,5-thiadiazole and 1,2,5-thiadiazole 1,1-dioxide moieties have been achieved, and are described herein. A 1,2,5-thiadiazole compound, [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (tdap), was used as a ligand to create multidimensional network structures based on S•••S and S•••N intermolecular interactions. A 1,2,5-thiadiazole 1,1-dioxide compound, [1,2,5] thiadiazolo[3,4-f][1,10]phenanthroline, 1,1-dioxide (tdapO2), was designed to create a stable radical anion, as well as good network structures. Single crystal X-ray structure analyses revealed that transition metal complexes of tdap, and radical anion salts of tdapO2 formed multidimensional network structures, as expected. Two kinds of tdap iron complexes, namely [Fe(tdap)2(NCS)2] and [Fe(tdap)2(NCS)2]•MeCN exhibited spin crossover transitions, and their transition temperatures showed a difference of 150 K, despite their similar molecular structures. Magnetic measurements for the tdapO2 radical anion salts revealed that the magnetic coupling constants between neighboring radical species vary from strongly antiferromagnetic (J = −320 K) to ferromagnetic (J = 24 K), reflecting the differences in their π overlap motifs. Full article
(This article belongs to the Special Issue Chalcogen-Nitrogen Chemistry)
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51 pages, 2445 KiB  
Review
Breathing Some New Life into an Old Topic: Chalcogen-Nitrogen π-Heterocycles as Electron Acceptors
by Anton V. Lonchakov, Oleg A. Rakitin, Nina P. Gritsan and Andrey V. Zibarev
Molecules 2013, 18(8), 9850-9900; https://doi.org/10.3390/molecules18089850 - 16 Aug 2013
Cited by 93 | Viewed by 9527
Abstract
Recent progress in the design, synthesis and characterization of chalcogen-nitrogen π-heterocycles, mostly 1,2,5-chalcogenadiazoles (chalcogen: S, Se and Te) and their fused derivatives, possessing positive electron affinity is discussed together with their use in preparation of charge-transfer complexes and radical-anion salts—candidate building blocks of [...] Read more.
Recent progress in the design, synthesis and characterization of chalcogen-nitrogen π-heterocycles, mostly 1,2,5-chalcogenadiazoles (chalcogen: S, Se and Te) and their fused derivatives, possessing positive electron affinity is discussed together with their use in preparation of charge-transfer complexes and radical-anion salts—candidate building blocks of molecule-based electrical and magnetic functional materials. Full article
(This article belongs to the Special Issue Chalcogen-Nitrogen Chemistry)
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