On the Crystal Structures of the Magnus Salts, Pt(NH3)4PtCl41

Atoji, Masao; Richardson, James W.; Rundle, R. E.

doi:10.1021/ja01569a009

Cited by 167 publications

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“…The slightly hygroscopic product is a brown powder having a metallic luster. The crystal structure of OO20-7608/80/0018-1533$0l .OO MGS was reported by Atoji et al [2]. The chain structure of MGSPOS, shown schematically in Figure 1, was proposed by Gitzel et al and supported by our x-ray and IR studies reported in our previous paper 131.…”

supporting

confidence: 78%

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt₆ (NH₃)₁₀Cl₁₀(HSO₄)₄

Kubota

Kobayashi

Tsujikawa

et al. 1980

Int J of Quantum Chemistry

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The salt Pt6(NH3) loCllo(HS04)4(MGSPOS) with the average valence of Pt 2.33 was prepared in powder form by means of partial oxidization of [Pt(NH3)4] [PtCI,](MGS) substituting HS04-for '/6 of both ligands NH3 and C1-. The electrical conductivity u has a maximum at about 230 K and a minimum at about 280 K. Therefore, the conductivity u is semiconductive with the gap energy 0.04 eV below 230 K, and metallic in the sense of du/dT < 0 between 230 and 280 K, and again semiconductive above 280 K. The thermal analysis by DSC shows only on heating, three anomalies, G at -1 50 K, A at -200 K, and B at -250 K.The exothermic anomaly A succeeding to the weak anomaly G indicates that a glass transition takes place, and endothermic anomaly B corresponds to a structural transition. These two transitions may correspond to the two metal-semiconductor transitions found in the u measurement. The ac calorimetry shows a specific heat anomaly also only on heating.Among the Pt complex salts that show quasi-one-dimensional electrical conductivity, the one most extensively studied is K2Pt(CN)4Bro.3-3H20 (KCP) in which interesting phenomena such as the Kohn anomaly and the Peierls distortion have been observed. However, the elucidation of its physical properties has not been exhaustive. Evidently, one of the reasons for the incompleteness may come from the fact that a random potential introduced by partially and randomly occupied sites of Br has a significant influence on conduction electrons. Therefore, as an example of a compound having no such randomness, we take the partially oxidized salt of the Magnus green salt [Pt(NH3)4] [PtCl,] (MGS), which has the formula Pt6(NH3)1oCllo(HS04)4, hereafter designated MGSPOS. We have studied physical properties of MGSPOS, and will report the results of measurements of the dc electrical conductivity and the thermal properties in this paper.MGSPOS was synthesized by the method of Gitzel et al.[ 11. The slightly hygroscopic product is a brown powder having a metallic luster. The crystal structure of ~

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supporting

confidence: 78%

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt₆ (NH₃)₁₀Cl₁₀(HSO₄)₄

Kubota

Kobayashi

Tsujikawa

et al. 1980

Int J of Quantum Chemistry

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confidence: 99%

“…[6][7][8][9][10][11] [3,5] MGS (see Fig. 1) and its derivatives consist of 1D arrays of platinum atoms, [6] with the interplatinum distance being the key geometric parameter responsible for the electrical properties. [5,10] either from simple electrostatics [7,9] or from supramolecular ordering, [12] depending on the length of the alkyl side group.…”

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confidence: 99%

Magnus' Green Salt Revisited: Impact of Platinum–Platinum Interactions on Electronic Structure and Carrier Mobilities

et al. 2006

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The quest for semiconducting materials that could combine high charge-carrier mobilities and ease of processability has recently triggered renewed interest [1][2][3][4][5] in a class of hybrid organic-inorganic materials that had been extensively studied several decades ago. [6][7][8][9][10][11] [3,5] MGS (see Fig. 1) and its derivatives consist of 1D arrays of platinum atoms, [6] with the interplatinum distance being the key geometric parameter responsible for the electrical properties. [5,10] either from simple electrostatics [7,9] or from supramolecular ordering, [12] depending on the length of the alkyl side group.However, a number of recent experimental observations warrant the establishment of more detailed electronic structureproperty relationships. For example, an n-type field-effect transistor fabricated from an MGS derivative with R = dmoc (3,7-dimethyloctyl) is inefficient, [3] although a wide, dispersive conduction band had been predicted by tight-binding band theory. [7,11] Also, the dmoc derivative exhibits much weaker interplatinum interactions than the eh derivative, where R = 2-ethylhexyl, in spite of the shorter interplatinum distance in the solid state (3.1 Å for dmoc-MGS versus 3.2 Å for eh-MGS), as evidenced by the respective chain lengths in solution: ca. 15 platinum atoms for dmoc-MGS versus ca. 470 platinum atoms for eh-MGS (the chain lengths are taken as a measure of the strength of the interplatinum interactions). [1,2] In this work, we investigate the geometric and electronic structure of MGS, taken as a model compound, by using density functional theory (DFT) in the framework of a planewave/pseudopotential implementation. First, we examine the interactions between the chloride and ammonia ligands, which are influenced by the interplatinum distance and/or alkyl substitution on the ammonia ligands. Secondly, we describe the main characteristics of the DFT electronic band structure, which allows us to identify the nature of the majority charge carrier and to predict the sensitivity of the carrier mobility to interplatinum separation. The theoretical findings are discussed in light of time-of-flight (TOF) measurements on the dmoc derivative.Geometry optimization of the tetragonal unit cell of the MGS crystal (see Fig. 1) was performed using the experimental lattice constants [6] under 3D periodic boundary conditions and reproduced very well the experimental geometric parameters. The calculated (experimental) values of the Pt-N and Pt-Cl bond lengths, for instance, are 2.077 (2.06) and 2.364 (2.34) Å, respectively (see Fig. 1b for other parameters). Calculations on isolated chains indicate that the crystal structure is well preserved (only weakly perturbed) in the absence of interchain interactions (Fig. 1a); in particular, the staggering angle j defined by the Cl-Pt-Pt-N dihedral angle, which could be sensitive to the surroundings, remains nearly intact (27.8°f or the isolated chain and 28.7°for the crystal). As a result, for the sake of simplicity, the remainder of our discussion will be...

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“…The differing optical properties of this compound are thus explained. The variation in structure is ascribed to packing effects.The crystal structure of Magnus' green salt, Pt(NH3)4PtCI4 and hereafter MGS, comprises chains of square-planar cations and anions.Sacked directly over one another, with a Pt-Pt sep~.ration of 3.26A (Atoji, Richardson & Rundle, 1957). Both the green colour and the dichroism exhibited by these crystals are distinct from those characteristic of the constituent ions (Yamada, 1951), and have been attributed to weak metal-metal bonding.…”

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The crystal structures of compounds analogous to Magnus' green salt

Cradwick¹,

Hall²,

Phillips³

1971

Acta Crystallogr Sect B

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Tetra(methylamine)platinum(II) chloroplatinate(II) and tetra(ethylamine)platinum(II) bromoplatinate(II) are confirmed as being isostructural with Magnus' green salt, Pt(NH3)4PtC14. The dimensions of the tetragonal cells are a=10.32, c=6.58, and a=12.27, c=6"71 A respectively; the space group is P4/mnc. Tetra(ethylamine)platinum(II) chloroplatinate(II) forms triclinic crystals, space group PI, with a=7.56, b=9"78, c=7.24 A, a=98"3 °, fl= 113"1 °, ~,= 103.4°; it has a similar structure in that cation and anion alternate in chains, but the cation is non-planar and orbital overlap between adjacent platinum atoms is inhibited. The differing optical properties of this compound are thus explained. The variation in structure is ascribed to packing effects.The crystal structure of Magnus' green salt, Pt(NH3)4PtCI4 and hereafter MGS, comprises chains of square-planar cations and anions.Sacked directly over one another, with a Pt-Pt sep~.ration of 3.26A (Atoji, Richardson & Rundle, 1957). Both the green colour and the dichroism exhibited by these crystals are distinct from those characteristic of the constituent ions (Yamada, 1951), and have been attributed to weak metal-metal bonding. The compound Pt(NH2CH3)4PtC14 is also green and similar in dichroism to MGS, but the analogues with higher amines are pink, and show only the dichroism of the chloroplatinate(II) ion. The methylamine compound is similar in powder diffraction pattern to MGS, whereas the ethylamine compound is not (Miller, 1961), and it has been assumed that steric effects inhibit the chain structure and thus prevent the metal-metal bond interaction• Subsequently it has been shown (Yamada, 1962(Yamada, , 1965) that crystals of Pt(amine)aPtBr4 and Pt(amine)aPtI4 are all abnormally coloured and dichroic, whether amine be ammonia, methylamine, ethylamine or various higher amines. This clearly indicated that the difference in structure of the higher amine chloroplatinates(II) is not caused by intra-chain steric interference, and Yamada (1965) suggested that it may be due to a weakening influence of the chlorine ligand on the metal-metal bond. This view is not supported * Present address" Chemistry Department, University of Auckland, Private Bag, Auckland, New Zealand.by reflectance spectra studies (Miller, 1965): nor indeed by Yamada's own single-crystal spectra, from which it is apparent that the band shifts are less and not greater in bromoplatinates(II) vis-d-vis chloroplatinates-(II). Further, the compounds Pt(NH3)4PtC14, Pt(NH3)4PdC14, Pd(NH3)4PtC14 and Pd(NH3)4PdC14 show varying spectral shifts, yet all have the MGS structure, with the same metal-metal separation (Miller, 1961(Miller, , 1965). It appears that chemical variations affect the optical phenomena far more than the crystal structure, and the difference in behaviour of tetra(ethylamine)platinum(II) chloroplatinate(II) remains anomalous. We have examined crystals of several of these compounds in an attempt to elucidate this problem.In each case, compounds were prepared by mixing solutions containing...

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On the Crystal Structures of the Magnus Salts, Pt(NH₃)₄PtCl₄¹

Cited by 167 publications

References 1 publication

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt₆ (NH₃)₁₀Cl₁₀(HSO₄)₄

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt₆ (NH₃)₁₀Cl₁₀(HSO₄)₄

Magnus' Green Salt Revisited: Impact of Platinum–Platinum Interactions on Electronic Structure and Carrier Mobilities

The crystal structures of compounds analogous to Magnus' green salt

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On the Crystal Structures of the Magnus Salts, Pt(NH3)4PtCl41

Cited by 167 publications

References 1 publication

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt6 (NH3)10Cl10(HSO4)4

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt6 (NH3)10Cl10(HSO4)4

Magnus' Green Salt Revisited: Impact of Platinum–Platinum Interactions on Electronic Structure and Carrier Mobilities

The crystal structures of compounds analogous to Magnus' green salt

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On the Crystal Structures of the Magnus Salts, Pt(NH₃)₄PtCl₄¹

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt₆ (NH₃)₁₀Cl₁₀(HSO₄)₄

Electrical and thermal properties of the partially oxidized salt of the magnus green salt with the formula Pt₆ (NH₃)₁₀Cl₁₀(HSO₄)₄