Structure of a Pt(II)-Pt(IY) Mixed-Valence Linear Chain Complex: Bis (1,2-diaminopropane )platinum(II)bis (1,2-diaminepropane ) - dibromoplatinum(IV)tetraperchlorate

[Pt(C3H10N2)2][Pt(C3H10N2)2Br2](ClO4)4 crystallizes as flat orthorhombic needles with cell dimensions: a = 7.74(1); b = 11.14(2); c = 19.42(3) Å, Z = 1. Since rotation photographs showed diffuse patterns corresponding to odd values of k without any Bragg reflections, the subcell for which b = 5.57(1) Å was adopted for the structural analysis; it has systematic absences consistent with space groups Pc 2 a and Pcma; the structure was refined in both space groups by least squares and difference Fourier syntheses to R = 0.062 in Pc 2a and R = 0.064 in Pcma. A final decision between the two space groups proved to be impossible within the scope of the experiment. An analysis of the “diffuse” layers reveals that the bridging bromines vibrate in a one-dimensional collective mode within a lattice of “uniform”, fixed platinum cations.

Download Full-text

Structure of the Linear-Chain Mixed Valence Compound Bis(l,3-diaminopropane)platinum(II)bis(l,3-diaminopropane)- diiodoplatinum(IV)tetraperchlorate

Zeitschrift für Naturforschung B ◽

10.1515/znb-1984-0213 ◽

1984 ◽

Vol 39 (2) ◽

pp. 197-200 ◽

Cited By ~ 2

Author(s):

Mario Cannas ◽

Giaime Marongiu ◽

Heimo J. Keller ◽

Barbara Müller ◽

Reinhold Martin

Keyword(s):

Structural Analysis ◽

Crystal Structures ◽

Satisfactory Agreement ◽

Title Compound ◽

Linear Chain ◽

Mixed Valence ◽

Space Groups ◽

Compound C ◽

Mixed Valence Compound

The title compound C12H49Cl4I2N8O 16Pt2, Mr 1314.1, is monoclinic P 21 (from structural analysis), a = 8.74(1), b = 11.36(1), c = 8.63(1), β = 107.6(5), V = 817 Å3, Z = 1, Dm (flotation) = 2.65 g cm-3, Dc = 2.66 g cm-3, MoKɑ λ = 0.71069, μ = 110.7 cm-1, R = 0.063 for 1068 observed reflections. Rotation photographs show diffuse patterns corresponding to odd values of k together with weak Bragg reflections. Refinement of diffractometer data was carried out in space groups Pm, P21/m and P21; both refinement in Pm and P21 give satisfactory agreement and lead to very similar crystal structures

Download Full-text

Ultrafast Vibrational Dynamics in a Quasi-One-Dimensional System: Femtosecond Impulsive Excitation of the PtBr(ethylenediamine) Mixed-Valence Linear Chain Complex

The Journal of Physical Chemistry A ◽

10.1021/jp993859f ◽

2000 ◽

Vol 104 (18) ◽

pp. 4308-4313 ◽

Cited By ~ 14

Author(s):

S. L. Dexheimer ◽

A. D. Van Pelt ◽

J. A. Brozik ◽

B. I. Swanson

Keyword(s):

Linear Chain ◽

Mixed Valence ◽

Chain Complex ◽

Dimensional System ◽

Vibrational Dynamics ◽

One Dimensional ◽

Impulsive Excitation

Download Full-text

A one-dimensional chloride-bridged PtII/PtIVmixed-valence complex with a 4-[(4-hydroxyphenyl)diazenyl]benzenesulfonate counter-ion

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229615019877 ◽

2015 ◽

Vol 71 (12) ◽

pp. 1033-1036 ◽

Cited By ~ 1

Author(s):

Nobuyuki Matsushita ◽

Ayako Taira

Keyword(s):

Valence State ◽

Title Compound ◽

Linear Chain ◽

Mixed Valence ◽

Chain Structure ◽

Structural Parameter ◽

One Dimensional ◽

Square Planar ◽

Cl Atoms ◽

Linear Chain Structure

The title compound,catena-poly[[[bis(ethylenediamine-κ2N,N′)platinum(II)]- μ-chlorido-[bis(ethylenediamine)platinum(IV)]-μ-chlorido] tetrakis{4-[(4-hydroxyphenyl)diazenyl]benzenesulfonate} dihydrate], {[PtIIPtIVCl2(C2H8N2)4](HOC6H4N=NC6H4SO3)4·2H2O}n, has a linear chain structure composed of square-planar [Pt(en)2]2+(en is ethylenediamine) and elongated octahedraltrans-[PtCl2(en)2]2+cations stacked alternately, bridged by Cl atoms, along thebaxis. The Pt atoms are located on an inversion centre, while the Cl atoms are disordered over two sites and form a zigzag ...Cl—PtIV—Cl...PtII... chain, with a PtIV—Cl bond length of 2.3140 (14) Å, an interatomic PtII...Cl distance of 3.5969 (15) Å and a PtIV—Cl...PtIIangle of 170.66 (6)°. The structural parameter indicating the mixed-valence state of the Pt atom, expressed by δ = (PtIV—Cl)/(PtII...Cl), is 0.643.

Download Full-text

Electronic and Resonance Raman Spectra of Some New Mixed-Valence Compounds of Pt and Pd with a Metal-Halide Chain

Zeitschrift für Naturforschung B ◽

10.1515/znb-1980-0606 ◽

1980 ◽

Vol 35 (6) ◽

pp. 676-679 ◽

Cited By ~ 7

Author(s):

G. C. Papavassiliou ◽

D. Layek

Keyword(s):

Raman Spectra ◽

Linear Chain ◽

Mixed Valence ◽

Resonance Raman ◽

Chain Structure ◽

One Dimensional ◽

Resonance Raman Spectra ◽

The One ◽

Mixed Valence Compounds ◽

Linear Chain Structure

Abstract The electronic and resonance Raman spectra of new mixed-valence compounds of the type M2ʹ[M(L)X3][M(L)X5], where Mʹ = K, NH4, M = Pt or Pd, L = NH3 or pyridine, and X = Cl, Br or I, have been studied. The single-crystal polarized reflectance spectra indicate the one-dimensional semiconductor behaviour. The polarized resonance Raman spectra confirm the --M(II)--X-M(IV)-X linear chain structure, which is in accordance with the X-ray results. The polarization of M-N bands can be explained by the Snyder's theory (1971).

Download Full-text

Vibrational studies of, and model for, halogen-bridged linear-chain mixed-valence complexes

Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences ◽

10.1098/rsta.1985.0014 ◽

1985 ◽

Vol 314 (1528) ◽

pp. 131-144 ◽

Cited By ~ 14

Keyword(s):

Resonance Raman Spectroscopy ◽

Linear Chain ◽

Mixed Valence ◽

Force Constants ◽

One Dimensional ◽

Moderate Resolution ◽

Vibrational Studies ◽

The One ◽

Expected Increase ◽

Chain Interaction

A number of complexes of the type [M II (LL) 2 ] [Pt IV (LL) 2 Cl 2 ] [ClO 4 ] 4 , where M = Ni, Pd or Pt and LL = 1,2-diaminoethane (en) or 1,2-diaminopropane (pn), as well as the monomers [Pt IV (LL) 2 Cl 2 ] Cl 2 and [M II (LL) 2 ] Cl 2 have been studied using Fourier transform infrared (f.t.i.r.) and resonance Raman spectroscopy. Under conditions of low tem perature and moderate resolution ( ca . 0.5 cm -1 ) it has proved possible to observe chlorine isotopic splitting in bands due to both the symmetric and the antisymmetric stretching modes of the linear Pt IV Cl 2 units in the chains. On the basis that the one-dimensional electronic properties of these chains are likely to be related to the in-chain Pt IV -Cl stretching force constants, a simple vibrational model is presented, which is able to reproduce the observed splitting patterns to well within experimental error. A comparative study of the Pt IV -Cl stretching force constants for the series of en complexes shows the trend: trans -[Pt IV (en) 2 Cl 2 ] Cl 2 (monomer) > Pd II - Pt IV > Ni II - Pt IV > Pt II −Pt lV . This trend is in line with that of the M II …Pt IV intervalence band maxima, namely Pd II - Pt IV (25000 cm -1 ) > Ni II - Pt IV (22200 cm -1 ) > Pt II - Pt IV (20800 cm -1 ), indicating an increase in M II … Cl chain interaction (and an expected increase in conductance) along the series.

Download Full-text

The red and near-infrared resonance Raman spectroscopy of photo-induced defects in the mixed-valence linear chain complex [PtII(en)2][PtIV(en)2Cl2][ClO4]4

Solid State Communications ◽

10.1016/0038-1098(90)90376-m ◽

1990 ◽

Vol 73 (7) ◽

pp. 521-525 ◽

Cited By ~ 23

Author(s):

Robert J. Donohoe ◽

R. Brian Dyer ◽

Basil I. Swanson

Keyword(s):

Raman Spectroscopy ◽

Near Infrared ◽

Resonance Raman Spectroscopy ◽

Linear Chain ◽

Mixed Valence ◽

Resonance Raman ◽

Chain Complex ◽

Induced Defects

Download Full-text

The crystal and molecular structure of tris(pentamethylenedithiocarbamate) chromium(III)-chloroform (1 : 2)

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19810006 ◽

1981 ◽

Vol 46 (1) ◽

pp. 6-19 ◽

Cited By ~ 5

Author(s):

Viktor Kettman ◽

Ján Garaj ◽

Jaroslav Majer

Keyword(s):

Molecular Structure ◽

Structural Analysis ◽

Crystal And Molecular Structure ◽

Analysis Method ◽

Complex Molecules ◽

Coordination Polyhedra ◽

X Ray ◽

Cell Dimensions ◽

Crustal Density ◽

Unit Cell Dimensions

The crystal and molecular structure of [Cr(S2CN(CH2)5)3].2 CHCl3 was found by the X-ray structural analysis method. The value R 0.090 was found for 1 131 observed independent reflections. The substance crystallizes in a space group of symmetry P212121 with the following unit cell dimensions: a = 0.8675 (6), b = 1.815(2), c = 2.155(3) nm. The experimentally observed crustal density was 1.48 Mgm-3 and the value calculated for Z = 4 was 1.51 Mgm-3. The CrS6 coordination polyhedron has the shape of a trigonally distorted octahedron, where the D3 symmetry is a approximately retained. The degree of trigonal distortion expressed as the projection of the chelate S-Cr-S angle onto the plane perpendicular to the C3 pseudo axis is Φ = 41.7° (Φ = 60° for an octahedron). The skeleton of the structure formed by the complex molecules contains channels filled with chloroform molecules. The specific type of complex-chloroform interaction consists of the formation of hydrogen bonds of the chloroform protons with the fully occupied pπ-orbitals of the sulphur atoms in the coordination polyhedra. The low stability and crystal decomposition can be explained by loss of chloroform from the channels.

Download Full-text