Single crystals of orthorhombic black phosphorus can be grown by a short way transport reaction from red phosphorus and Sn/SnI 4 as mineralization additive. Sizes of several millimeters can be realized with high crystal quality and purity, making a large area preparation of single or multilayer phosphorene possible. An in situ neutron diffraction study has been performed addressing the formation of black phosphorus. Black phosphorus is formed directly via gas phase without the occurrence of any other intermediate phase. Crystal growth was initiated after cooling the starting materials down from elevated temperatures at 500 °C. Highlights:-Large black phosphorus crystals were grown by a short way transport reaction -In situ neutron diffraction affirm the formation of black P directly from gas phase -Large crystals can be used as starting material for phosphorene synthesis

NaP 7 is a phosphorus-rich polyphosphide featuring a helical polyphosphide substructure. It can be prepared from the elements as well as via short way transport using CuI as mineralizer additive. As a potential intermediate compound during the reaction of phosphorus with sodium in sodium ion batteries, we investigated the structural and * Prof. Dr. T. Nilges Fax: +49-89-289 13762 E-Mail: tom.nilges@lrz.tum.de [a] Synthese und Charakterisierung innovativer Materialien 1395 physical properties of this polyphosphide in detail. X-ray single crystal and powder data were collected and the structure was re-determined. Thermal properties were measured and the electronic structure was calculated using DFT methods. NaP 7 is a semiconductor featuring a bandgap in the visible light region.

AgP15 was synthesized from the elements via a short-way transport reaction following the mineralizer concept. The needle-shaped crystals were characterized by single-crystal and powder X-ray diffraction. It crystallizes triclinically in space group P1̅ with cell parameters of a = 6.937(1) Å, b = 9.000(1) Å, c = 11.103(2) Å, α = 99.95(1)°, β = 99.61(1)°, and γ = 105.980(9)°. AgP15 exhibits a tubular phosphorus substructure related but neither isotypic nor isostructural to the alkaline phosphides MP15 (M = Li-Rb). The thermal properties, electronic structure, and experimental band gap of this new semiconductor have been determined. Finally, Raman spectra of AgP15 and selected alkaline-metal polyphosphides MP15 have been measured and interpreted. AgP15 represents the first transition-metal representative of this class of materials.

NaCd4P3 and NaCd4As3 were synthesized via short-way transport using the corresponding elements and CdI2 as mineralizer. At room temperature, the two β-polymorphs adopt the RbCd4As3 structure type which has been recently reported for alkali metal (A)-d(10) transition metal (T)-pnictides (Pn). The title compounds crystallize rhombohedrally in space group R3̅m at room temperature and show reversible phase transitions to incommensurately modulated α-polymorphs at lower temperatures. The low-temperature phases are monoclinic and can be described in space group Cm(α0γ)s with q vectors of q = (-0.04,0,0.34) for α-NaCd4P3 and q1 = (-0.02,0,0.34) for α-NaCd4As3. Thermal properties, Raman spectroscopy, and electronic structures have been determined. Both compounds are Zintl phases with band gaps of 1.05 eV for β-NaCd4P3 and ∼0.4 eV for β-NaCd4As3.

Synthesis, Structure, and Properties of NaP 7, a Phosphorus-rich Polyphosphide. -NaP 7 is prepared from stoichiometric quantities of red phosphorus and Na in the presence of purified CuI as mineralizer (evacuated graphitized silica tubes, 823 K, 7 d). The compound crystallizes in the tetragonal space group I4 1/acd with Z = 16 (single crystal XRD). The structure consists of  1 ] helical tubes running along the c axis. The compound decomposes peritectically into white phosphorus, Na 3P11, and Na3P7. DFT calculations show that NaP 7 is a semiconductor featuring an optical bandgap of 1.71-1.82 eV in the visible light region. -(GROTZ, C.; KOEPF, M.; BAUMGARTNER, M.; JANTKE, L.-A.; RAUDASCHL-SIEBER, G.; FAESSLER, T. F.; NILGES*, T.; Z. Anorg. Allg. Chem. 641 (2015) 8-9, 1395-1399, http://dx.