Phosphorus Nanorods—Two Allotropic Modifications of a Long‐Known Element

Pfitzner, Arno; Bräu, Michael F.; Zweck, Josef; Brunklaus, Gunther; Eckert, Hellmut

doi:10.1002/ange.200460244

Cited by 68 publications

(46 citation statements)

References 16 publications

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“…Recently, the ]P4(4)[P8] and ]P2-A C H T U N G T R E N N U N G [P10] chains were isolated from the copper halide matrix, resulting in phosphorus nanorods. [19,20] The nanorods show parallel arrangement in HRTEM images, crystal structure thus far being unavailable.…”

Section: Introductionmentioning

confidence: 99%

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

Karttunen

Linnolahti

Pakkanen

2007

Chemistry A European J

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The existence of two new allotropic forms of phosphorus, icosahedral cages and ring-shaped chains, is predicted. The cages and rings are nanostructural modifications of the black and the red phosphorus, respectively. The icosahedral and ring-shaped allotropes are compared with the experimentally known allotropic forms of phosphorus by quantum chemical methods. Both the cages and the rings are thermodynamically favored over the white phosphorus, the rings being comparable to the Hittorf's violet phosphorus and to the recently discovered fibrous red phosphorus. The stabilities of the icosahedral cages increase as a function of their size, having structural resemblance with the rhombohedral black phosphorus. The high thermodynamic stability of the phosphorus nanostructures suggests their experimental synthesis to be viable.

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Section: Introductionmentioning

confidence: 99%

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

Karttunen

Linnolahti

Pakkanen

2007

Chemistry A European J

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“…[10] Various forms of red phosphorus have been classified in a comprehensive theoretical study. [11] The copper halide matrix techniques used to prepare red phosphorus chains have also been applied to obtain mixed PAs chains with arsenic contents of up to 55 %.…”

Section: Introductionmentioning

confidence: 99%

Icosahedral and Ring‐Shaped Allotropes of Arsenic

2007

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We predict the existence of two novel families of arsenic nanostructures: icosahedral cages and ring-shaped chains. Quantum chemical calculations on the cages, rings, and the experimentally known allotropes of arsenic suggest the nanostructures to be thermodynamically stable. The icosahedral cages are modifications of the gray allotrope of arsenic, while the ring-shaped chains are structurally related to the red allotrope of phosphorus. Comparisons between the analogous allotropes of arsenic and phosphorus show distinct differences. While phosphorus favors the ring-shaped chains over the icosahedral cages, large cages become favorable for arsenic. From the thermodynamical point of view, experimental preparation of the proposed families of arsenic nanostructures is expected to be viable.

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“…Recently, it has been shown that the pnicogen chains in both (CuI) 8 P 12 and (CuI) 8 P 7.2 As 4.8 can effectively be liberated from the CuI host by treatment with aqueous potassium cyanide, producing novel allotropes of phosphorus and binary P-As, respectively. [13,14] Although each pnicogen position in (CuI) 8 P 7.2 As 4.8 has shared occupancy of both P and As, the "roof" positions in the [Pn8] cages (indicated by * in Figure 1) appear to be As rich, suggesting that these are not true solid solutions, but that there are preferred sites for As within the structure. Furthermore, the Cu I lattice in the 40 % As phase shows increased disorder relative to the parent compound, suggesting that As substitution may lead to augmented copper ion conductivity.…”

Section: Planar Squaresmentioning

confidence: 99%

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Jayasekera

Brock

et al. 2005

Chemistry A European J

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A series of P/As mixed pnicogen phases of composition (CuI)(8)P(12-x)As(x), in which x = 2.4, 4.2, 4.8, 5.4, and 6.6, have been synthesized and characterized by X-ray single crystal and powder diffraction, solid-state NMR spectroscopy, thermal gravimetric analysis, and impedance spectroscopy. These materials are isostructural to (CuI)(8)P(12) and consist of neutral, tubular P/As mixed pnicogen chains associated with Cu(I) and I(-) ions. The As is distributed throughout the pnicogen chains; however, the "roof" sites of the [P8] cage show preferred occupation by As relative to the other sites. Accordingly, the change in cell volume is not a linear function of the As incorporation. Solid-state (31)P NMR spectroscopy of the 40 % As incorporated sample are consistent with the X-ray structural model, with extensive broadening due to (31)P-(75)As coupling and site disorder, and a change in the chemical shifts of the resonances due to the As substitution into the lattice. The degree of copper ion site disorder, probed by single-crystal X-ray diffraction, increases with increasing As content. Although very little change is observed in the copper ionic conductivity of polycrystalline samples, which ranges from 1.8-5.1 x 10(-6) S cm(-1) for (CuI)(8)P(12-x)As(x), x = 0, 4.2, 5.4; a single crystal (x = 4.8) measured along the needle axis has a conductivity of 1.7 x 10(-3) S cm(-1) at 128 degrees C. This represents an order of magnitude improvement in conductivity over (CuI)(8)P(12) at the same temperature.

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Phosphorus Nanorods—Two Allotropic Modifications of a Long‐Known Element

Cited by 68 publications

References 16 publications

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

Icosahedral and Ring‐Shaped Allotropes of Arsenic

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

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Phosphorus Nanorods—Two Allotropic Modifications of a Long‐Known Element

Cited by 68 publications

References 16 publications

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

Icosahedral and Ring‐Shaped Allotropes of Arsenic

Structure–Property Correlations in Solid Solutions of (CuI)8P12−xAsx, 2.4≤x≤6.6

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Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6