Indium Iodide Research Articles

ChemInform Abstract: The Preparation and Vapor Pressures of the Indium(I) Halides and the Standard Molar Gibbs Free Energy Change for Formation of InX from In(g) and X2(g) (X: Cl, Br, or I)

ChemInform Abstract: The Preparation and Vapor Pressures of the Indium(I) Halides and the Standard Molar Gibbs Free Energy Change for Formation of InX from In(g) and X2(g) (X: Cl, Br, or I)

Newly observed lines and hyperfine structure in the infrared spectrum of indium obtained by using a Fourier-transform spectrometer

The spectrum of neutral indium has been studied in the infrared region by means of the Fourier-transform spectrometer at the Laboratoire Aime Cotton, Orsay, France. A microwave-excited discharge tube containing indium iodide was used as the light source. A total of ten hyperfine structures was studied. Precise measurements of the center of gravity of the structures give energy levels with an error less than 0.005 cm−1. Complete analysis of these hyperfine structures resulted in the determination of the magnetic-dipole and electric-quadrupole interaction constants for one odd and four even levels. The observation also resulted in the measurements of 57 lines in the region of 0.86–4.0 μm, and, of these, 41 lines were observed for the first time to our knowledge.

Raman spectroscopic investigations of concentrated aqueous solutions of InCl3 and of InBr3

Raman spectra have been observed for concentrated solutions of indium chloride and bromide in water and deuterium oxide. Isotopic shifts and the modification of these profiles were observed for the Raman bands at ca. 400 cm–1, 195 cm–1, 60–80 cm–1 in indium bromide, and ca. 400 cm–1, 295 cm–1, 90–120 cm–1 in indium chloride solutions. When the static pressure of the solution increases from 1 atmosphere up to ca. 6 kbar the value of the frequency of the 195 cm–1 Raman band increases and a small modification of the profile of the spectrum of the ca. 4 mol dm–3 indium bromide solution is observed in the region near 40 cm–1. Indium complexes with a quasi-linear configuration (halide–indium–halide) seem to be the predominant species existent in these concentrated solutions; the presence of coordinated water molecules in these complexes is apparent.

ChemInform Abstract: A Barbier Allylation and a Reformatsky Reaction of Carbonyl Compounds Mediated by Indium(I) Iodide.

AbstractThirteen carbonyl compounds such as (I) are coupled with allyl iodide (II) in the presence of indium(I) iodide to give the homoallylic alcohols (III).

The preparation and vapour pressures of the indium(I) halides and the standard molar Gibbs free energy change for formation of InX from In(g) and X 2(g), (X = Cl, Br, or I)

The syntheses of high-purity InCl, InBr, and InI from the elements are outlined. The vapour pressures above the liquid indium(I) halides have been measured by the quasistatic method over the ranges: InCl, 528 to 914 K; InBr, 569 to 950 K; and InI, 646 to 958 K. The molar enthalpies of evaporation of the indium(I) halides have been calculated by the second-law and third-law methods. The temperature variation of the changes in the standard molar Gibbs free energies for the formation of InX(s), InX(1), and InX(g), (X = Cl, Br, or I), from the gaseous elements have been derived.

A Barbier allylation and a Reformatsky reaction of carbonyl compounds mediated by indium(I) iodide

Indium(I) iodide was found to mediate in the Barbier allylation and in the Reformatsky reaction of aldehydes and ketones to give homoallylic alcohols and β-hydroxy esters, respectively, presumably via allylindium(III) diiodide.

Electron-diffraction studies on the In-I system. IV. Geometrical configuration, vibrational frequencies, and molecular energetics for indium iodide

A survey is presented on electron diffraction by Inl, In13, In21~, Inlnl 4 and on the vapor compositions above indium monoiodide, diiodide, and triiodide. The molecular structures are examined and relationships are derived between the structure parameters. Estimates are made for the lacking vibrational frequencies of In21s, and band assignments are made for Inlnl 4. The electron-diffraction data give the enthalpy and entropy of 21nl 3 $ !n216 and Inl + Inl 3 $ InInl~, from which the heats of formation of gaseous In216 and Inlnl~ can be calculated. These molecules show a correlation between the mean bond energies and the structural characteristics. Heats of reaction are derived for reactions involving indium io ~ dides.

Coordination compounds of indium. Part 44. The oxidation of indium(I) halides by tetrahalogeno-ortho-quinones

The reaction of indium(I) halides (InX; X = Cl, Br, I) with tetrahalogeno-ortho-quinones (Y4C6O2; Y = Cl, Br) gives the oxidative addition product Y4C6O2InX, These compounds have been isolated as adducts with neutral bidentate donor ligands (N,N,N′,N′-tetramethylethanediamine (tmen), 1,10-phenanthroline) or as salts of the anionic complexes [Y4C6O2InCl2]− or [Y4C6O2In(Cl)Br]−. The number of coordinated tmen molecules, and hence the structure, depends on the method of preparation. Infrared, 1H NMR, and 13C NMR spectroscopy all confirm that these products are all substituted-catecholato derivatives of indium(III), and the structure of these various neutral or anionic derivatives is discussed. The temperature dependence of the 13C NMR spectra shows that the dynamic behaviour of these compounds (in d6-dmso) is similar to that observed in previous studies of indium(III) chelate complexes.

Indium(III) halide complexes with trimethylphosphine sulphide and trimethylarsine sulphide: structures and bonding of [InX3(Me3MS)2](X = Cl or Br, M = P or As) and [InCl3(H2O)(Me3AsS)2

The crystal structures of four isomorphous compounds [InX3(Me3MS)2], with X = Cl or Br and M = P or As, and of a related octahedral complex [InCl3(H2O)(Me3AsS)2] are described. In the isomorphous series, the indium is in a distorted trigonal-bipyramidal co-ordination with the thio ligands in apical positions. The distortions, which include small differences in the lengths of the two In–S bonds in each molecule, are produced by a combination of intra- and inter-molecular repulsions. The average In–S bond lengths for each molecule show qualitative decrease with the increasing charge transfer to be inferred from ligand polarity and halogen electronegativity. Comparison with bond lengths in the octahedral complex [InCl3(H2O)(Me3AsS)2] shows the characteristic lengthening of the apical trigonal-bipyramidal bonds. The M–S bonds of the ligands show the usual lengthening upon co-ordination, with a moderate fall in bond order, e.g. from 2.0 to 1.6 in [InCl3(Me3PS)2]. 31P N.m.r. spectra also point to a reduction in the π character of the P–S bonds. There is no evidence for the use of In d orbitals in the In–S bond.

The spectra and structure of indium iodide: Potential energy curves and dissociation energies of the X 0 +, A 0 +, and B 1 states

Rotational constants for the A 0 + and B 1 states reported previously have been slightly revised as a result of the analysis of a further sixteen bands in the A 0 +- X 0 + and B 1- X 0 + band systems. Potential energy curves have been constructed on the basis of the revised molecular constants. A discussion of the nature of the chemical bond in InI and the possible correlation to dissociation products has led to a revised value of 27 500 cm −1 for the dissociation energy of ground state InI.

Dynamical aspects of edge luminescence in orthorhombic InI

Edge luminescence in orthorhombic indium iodide has been investigated under pulsed dye laser excitation at liquid helium temperature. Emission spectra consist of several lines with approximately the LO phonon energy spacing C̵ω LO (13.8 meV). Time-resolved spectra reveal bound exciton (BE) luminescence and donor-acceptor (DA) pair recombination luminescence. The spectral shape changes strongly with time. The fast component (τ<10 ns) consists of the bound exciton BE 0 peak followed by LO-phonon side bands. The slow component (τ<100 ns) is composed of a no-phonon component DA 0 followed by several LO-phonon replicas. This series of peaks shifts to lower energy with time. An anti-Stokes component appears at the DA 0 peak with significant intensity for the laser energy lower than that of the first member of the series, DA 0. This component is interpreted to originate from the cascade excitation of electrons (holes) at deeper traps.

Multiple LO Phonon Scattering in Orthorhombic Thallous Iodide

The scattering spectrum of orthorhombic TlI has been measured at 2 K under the resonant excitation around the first exciton energy of 2.87 eV. The spectrum is composed of multiple LO phonon lines showing a characteristic intensity alternation as was found in indium halides. The dependence of intensities of the LO lines on the incident photon energy has been investigated. The LO lines show a resonant enhancement in intensity with 2 s and higher exciton states as well as with the 1 s exciton state. It is also found that some of the excitons relaxed to the band bottom are transformed into photons with the emission of 2LO phonons rather than 1LO phonon.

The insertion of indium(I) halides into the MX bond of some main group organometallic halides

Indium(I) halides (InX) react with Ph 3SnX (X = Cl, Br, I) in toluene/tmed mixtures to give Ph 3SnInX 2·tmed compounds (tmed = N, N, N′, N′-tetramethylethanediamine), and Ph 3Sn(OAc) yields Ph 3SnIn(OAc)X 2·tmed. Vibrational spectra and conductivities of these compounds, and of the salt Et 4N[Ph 3SnInCl 3], show that these are the first examples of SnIn bonded molecules. With Me 3SnCl, Ph 3SnH, Ph 3GeCl, Ph 3PbCl and Ph 2PCl, no oxidative addition reaction was observed. The results are compatible with previous discussions of the mechanism of such reactions, based on the insertion of indium into the MX bond.

The spectra and structure of indium iodide: The rotational and vibrational constants of the B 1 state

The rotational constants of the B 1 state of indium iodide are reported for the first time as B e = 0.037533 cm −1 and α e = 0.000289 cm −1 while T e = 25050.60 cm −1 for the B1- X0 + transition. Accurate vibrational constants are also computed from measured Q heads as ω e= 146.36 cm −1 and ω e χ e = 2.20 cm −1.

The spectra and structure of indium iodide: The rotational and vibrational constants of the A0 + state

The rotational constants of the A0 + state of InI are reported for the first time as B e = 0.038077 cm −1 and α e = 0.0002373 cm −1, while T e = 24402.91 cm −1 for the A0 +- X0 + transition. Accurate vibrational constants for both the A0 + and X0 + states are computed from the derived band origins.

Dry etching of indium phosphide

In contrast to other III–V materials such as gallium arsenide, it is difficult to dry-etch indium phosphide, particularly if it is desired to use organic mask materials which deform at relatively low temperatures. Argon ion beams usually sputter phosphorus preferentially, and the common reactive dry etchants which contain fluorine and chlorine produce indium halides which are not volatile unless heated to over 150°C. This paper discusses low-temperature reactive-ion etching (RIE) and ion-beam assisted etching (IBAE) processes, using iodine (and in one case, chlorine) chemistry combined with low-energy (<500 eV) ionic bombardment and shows that InP may be dry-etched with good anisotropy, smooth stoichiometric surfaces and little crystal damage.

Synthesis and properties of InxMo6Se8-yIy indium insertion compounds

We present a study of the properties of the series InxMo6Se8-yIy (y=0.5, 1.0, 2.0) having the hexagonal-rhombohedral Mo6Se8 structure type. The materials were prepared by a low temperature (525 °C) insertion technique. For y=0.5, only the new superconducting phase In.5Mo6Se7.5I.5 was found. For y=1.0 and y=2.0, the InxMo6Se8-yIy phases represent the first Chevrel phases which are solid solutions with respect to indium insertion. InxMo6Se7I (0 < × < 1) presents a phase diagram which indicates phenomena associated with an In+1-In+3 valence change as x increases. InxMo6Se6I2 (0 < × < 0.66) is a well-behaved solid solution of In3+ in Mo6Se6I2. For both y=1.0 and y=2.0, an increase in In3+ concentration increases the rhombohedral angle into the 94°– 95° range and the hexagonal unit cell volumes into the range of 940 Å 3 at maximum indium concentrations. At higher temperatures, the indium abstracts iodide from the cluster units which then condense to form known phases with larger clusters. Even though Mo6X8 phases are stabilized by partial halogen substitution, attempts to synthesize niobium Chevrel-type phases stabilized by halogen-chalcogen substitution were unsucessful.

Electrical conductivity of iodine-, iron chloride- and indium iodide-doped polyacetylene

The temperature dependence of the d.c. electrical conductivity of polyacetylene doped with iodine, iron chloride and indium iodide, respectively, is investigated and the influence of the dopant species and concentration is studied. It is found that for a rough characterization, in all cases σ( T) can be approximated by the phenomenological relation σ(T) ∼ σ 0 exp[−( T 0 T ) ν] with ν ∼ 1 3 (fits with ν = 1 2 or ν = 1 4 not being significantly worse). In addition, there exists a strong correlation between σ 0 and T 0. The results imply that the conductivity of doped polyacetylene cannot be described by the percolation of a stoichiometrically oxidized phase in an insulating matrix of pristine polymer.

Multiple LO scattering in indium iodide

Resonant secondary emission is investigated in the energy range around the direct exciton in orthorhombic InI. Spectra at liquid nitrogen temperature exhibit multiple LO lines with characteristic intensity alternation as in InBr at 2K. Incident photon energy dependence of their scattering intensities is also studied. Pronounced outgoing resonance with 1 s exciton is found in each LO line.

Bond properties of anionic mixed halogeno-complexes InX3Y- (X ≠ Y = Cl, Br, I)

The normal coordinate analysis has been performed for the anionic mixed halogeno-complexes InX3Y- (X ≠ Y = Cl, Br, I). The trends among the force constants are discussed and the assignments of the observed fundamental frequencies are examined thoroughly. It has been found that the present analysis provides reliable data to introduce a light into the bond properties of InX3Y- ions. In addition to this the mean amplitudes of vibrations, bond order and bond polarizability derivatives have been studied for the systems under investigation and a comparison of bond parameters among the halides of indium are made.