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

Svensson, Per H LU (1998)
Abstract
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... (More)
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. (Less)
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author
opponent
  • Professor Klapötke, Thomas M., Institut für Anorganische Chemie der Ludwig-Maximilians-Universität, München
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Quantum chemical calculations, vibrational spectroscopy, EXAFS, X-ray diffraction, charge-transfer, Polyiodides, binary metal iodide-iodine systems, Organisk kemi, Organic chemistry
pages
290 pages
publisher
Inorganic Chemistry, Chemical Center, Lund University
defense location
sal D, Chemical Center
defense date
1998-10-10 10:15
external identifiers
  • Other:ISRN: LUN KDL/NK00--98/1032--SE
language
English
LU publication?
yes
id
e516979e-9b3e-4763-aa46-aa0c350102b8 (old id 38922)
date added to LUP
2007-10-14 17:43:32
date last changed
2016-09-19 08:45:13
@misc{e516979e-9b3e-4763-aa46-aa0c350102b8,
  abstract     = {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.},
  author       = {Svensson, Per H},
  keyword      = {Quantum chemical calculations,vibrational spectroscopy,EXAFS,X-ray diffraction,charge-transfer,Polyiodides,binary metal iodide-iodine systems,Organisk kemi,Organic chemistry},
  language     = {eng},
  pages        = {290},
  publisher    = {ARRAY(0x973be58)},
  title        = {Synthesis, Structure and Bonding in Polyiodides and Binary Metal Iodide-Iodine Systems},
  year         = {1998},
}