Synthesis, Structure and Bonding in Polyiodides and Binary Metal Iodide-Iodine Systems

Per H Svensson

Forskningsoutput: AvhandlingDoktorsavhandling (sammanläggning)

Sammanfattning

Polyiodides and binary metal iodide-iodine compounds have been prepared and investigated by means of X-ray diffraction, EXAFS, far-IR, Raman, UV-vis and NMR spectroscopy and quantum chemical calculations. (Et3S)[AuI4].2I2 and (Me3S)[Cd2I6]1/2.3I2 were synthesised through the reaction between the room temperature melt of trialkylsulfonium polyiodides and the corresponding metal iodides. The structure of (Et3S)[AuI4].2I2 consists of AuI4- units coordinated by I2 forming infinite zigzag chains, while (Me3S)[Cd2I6]1/2.3I2 has a network structure. [hmtH]2(Hg2I6)1/2(HgI3).1/2I2, stable at ambient conditions, was made through the reaction between hmt.HgI2 and HI. The structure consists of infinite linear chains of iodine coordinated to the bridging iodide of Hg2I62-. Raman and far-IR spectra of the binary metal iodide-iodine compounds show features in the 180 cm-1 region characteristic for charge-transfer coordinated iodine. The polyiodide (Me3S)3I26 was prepared by the reaction between TlI and (Me3S)I7. The structure consists of a complicated network. A spectroscopic and quantum chemical study of the trialkylsulfonium polyiodide reaction medium indicate that the spectral features can be explained by the presence of both asymmetric and symmetric triiodides and a small amount of higher polyiodides formed by the decomposition of the triiodide. These results were also supported by the spectroscopic and structural investigation of dibenzo-18-crown-6 polyiodides and mixed polyhalides. A quantum chemical study of polyiodides and gold iodides shows that they are closely related and that AuI2- and AuI4- are appropriate guest molecules in polyiodide structures. A structural statistical and quantum chemical investigation of the intermolecular bonding in polyiodides indicate that these are best characterised as weak covalent bonds. (DodMe2)SI has a bilayered structure which indicate potential use as medium for inorganic liquid crystals based on the corresponding polyiodides.
Originalspråkengelska
KvalifikationDoktor
Tilldelande institution
  • Kemiska institutionen
Handledare
  • [unknown], [unknown], handledare, Extern person
Tilldelningsdatum1998 okt. 10
Förlag
StatusPublished - 1998

Bibliografisk information

Defence details

Date: 1998-10-10
Time: 10:15
Place: sal D, Chemical Center

External reviewer(s)

Name: Klapötke, Thomas M.
Title: Professor
Affiliation: Institut für Anorganische Chemie der Ludwig-Maximilians-Universität, München

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Article: I Trimethylsulfonium BromidePer H. Svensson and Lars A. Bengtsson-KlooActa Cryst. C52 (1996) 2580.

Article: II A Vibrational Spectroscopic, Structural and QuantumChemical Study of the Triiodide ionPer H. Svensson and Lars KlooManuscript.

Article: III Investigations of the Polyiodides H3O.Ix (x= 3, 5 or 7) asDibenzo-18-Crown-ComplexesLars Kloo, Per H. Svensson and Michael J. TaylorManuscript.

Article: IV What is an Intermolecular I-I Bond ?Lars Kloo, Jan Rosdahl and Per H. SvenssonManuscript.

Article: V Metal Iodides in Polyiodide Networks - The Structural Chemistry ofComplex Gold Iodides with Excess of IodinePer H. Svensson, Jan Rosdahl and Lars Bengtsson-KlooEur. J. Chem., in press.

Article: VI Bis(triethylsulfonium) Tetraiodocadmate(II)Lars Bengtsson-Kloo, Johan Berglund, Harald Stegemann, Christer Svensson and Per H. SvenssonActa Cryst. C52 (1996) 3045.

Article: VII Metal Iodides in Polyiodide Networks - The Structural Chemistry of CdI2 with Excess of IodinePer H. Svensson, Lars Bengtsson-Kloo and Per PerssonJ. Chem Soc., Dalton Trans., (1998) 1425.

Article: VIII Bis(triethylsulfonium) Tetraiodomercurate(II)Lars Bengtsson-Kloo, Johan Berglund, Harald Stegemann, Christer Svensson and Per H. SvenssonActa Cryst., in press.

Article: IX (Hexamethylenetetraamine)diiodomercury(II), HgI2.hmtPer H. Svensson and Lars A. Bengtsson-KlooActa Cryst. C51 (1995) 2289.

Article: X Metal Iodides in Polyiodide Networks - Synthesis of BinaryMetal Iodide-Iodine Compounds Stable at Ambient ConditionsPer H. Svensson and Lars KlooInorg. Chem., submitted.

Article: XI Metal Iodides in Polyiodide Networks - The Structural Chemistry of Complex Thallium Iodides with Excess of IodinePer H. Svensson, Günther Raud and Lars KlooManuscript.

Article: XII Structural Investigations of the Dodecyldimethylsulfonium Polyiodides (C12H25)(CH3)2SIx (x=3-11) - Potential Inorganic Liquid Crystalline MaterialsPer H. Svensson and Lars KlooManuscript.


The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Inorganic chemistry (ceased) (LUR000010)

Ämnesklassifikation (UKÄ)

  • Oorganisk kemi

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