Transformation of Ammonium Dicyanamide into Dicyandiamide in the Solid

Ammonium dicyanamide NH4[N(CN)2] was synthesized through aqueous ion exchange. The crystal structure was investigated by single-crystal X-ray diffraction (P21/c, a = 378.67(6) pm, b = 1240.9(3) pm, c = 911.84(14) pm, β = 91.488(18)°, Z = 4). It derives from the CsCl structure type. Medium strong hydrogen bonds between NH4+ and [N(CN)2]- ions are indicative of the observed formation of dicyandiamide H4C2N4 during heating. According to DSC and temperature-dependent X-ray powder diffractometry, this isomerization is exothermic and occurs between 102 and 106°C in the solid. The reaction represents the isolobal analogue to the classical synthesis of urea by heating NH4OCN. While other alkali and alkaline earth dicyanamides undergo trimerization or polymerization of their anions during heating, ammonium dicyanamide thus shows a different reactivity

A Carbon Nanofilament-Bead Necklace

Carbon nanofilaments with carbon beads grown on their surfaces were successfully synthesized reproducibly by a floating catalyst CVD method. The nanofilaments hosting the pearl-like structures typically show an average diameter of about 60 nm, which mostly consists of low-ordered graphite layers. The beads with diameter range 150−450 nm are composed of hundreds of crumpled and random graphite layers. The mechanism for the formation of these beaded nanofilaments is ascribed to two nucleation processes of the pyrolytic carbon deposition, arising from a temperature gradient between different parts of the reaction chamber. Furthermore, the Raman scattering properties of the beaded nanofilaments have been measured, as well as their confocal Raman G-line images. The Raman spectra reveal that that the trunks of the nanofilaments have better graphitic properties than the beads, which is consistent with the HRTEM analysis. The beaded nanofilaments are expected to have high potential applications in composites, which should exhibit both particle- and fiber-reinforcing functions for the host matrixes

[(Li0.8Fe0.2)OH]FeS and the ferromagnetic superconductors [(Li0.8Fe0.2)OH]Fe(S1-xSex) (0<x<1)

[(Li0.8Fe0.2)OH]FeS and the series [(Li0.8Fe0.2)OH]Fe(S1-xSex) (0<x<1) were synthesized by hydrothermal methods and characterized by X-ray single crystal and powder diffraction, EDX and chemical analysis. Selenium-rich compounds show the coexistence of magnetic ordering with superconductivity known from the pure selenium compound. Sulphur doping decreases the critical temperature through chemical pressure until superconductivity is completely absent in [(Li0.8Fe0.2)OH]FeS, while the ferromagnetism in the [(Li0.8Fe0.2)OH] layers persists. The Li:Fe ratio in the hydroxide layer, and thus the charge transfer of 0.2 electrons from the hydroxide to the iron chalcogenide layers remains unchanged in [(Li0.8Fe0.2)OH]Fe(S1-xSex), which indicates that the chemical pressure effect of the smaller sulphide ions impedes superconductivity in [(Li0.8Fe0.2)OH]FeSComment: 4 pages, 5 Figure

Fullerene van der waals Oligomers as electron traps

Density functional theory calculations indicate that van der Waals fullerene dimers and larger oligomers can form interstitial electron traps in which the electrons are even more strongly bound than in isolated fullerene radical anions. The fullerenes behave like super atoms , and the interstitial electron traps represent one-electron intermolecular σ-bonds. Spectroelectrochemical measurements on a bis-fullerene-substituted peptide provide experimental support. The proposed deep electron traps are relevant for all organic electronics applications in which non-covalently linked fullerenes in van der Waals contact with one another serve as n-type semiconductors

Exciton Energy Transfer in Pairs of Single-Walled Carbon Nanotubes

We studied the exciton energy transfer in pairs of semiconducting nanotubes using high-resolution optical microscopy and spectroscopy on the nanoscale. Photoluminescence from large band gap nanotubes within bundles is observed with spatially varying intensities due to distance-dependent internanotube transfer. The range of efficient energy transfer is found to be limited to a few nanometers because of competing fast nonradiative relaxation responsible for low photoluminescence quantum yield

Antenna-enhanced Optoelectronic Probing of Carbon Nanotubes

We report on the first antenna-enhanced optoelectronic microscopy studies on nanoscale devices. By coupling the emission and excitation to a scanning optical antenna, we are able to locally enhance the electroluminescence and photocurrent along a carbon nanotube device. We show that the emission source of the electroluminescence can be point-like with a spatial extension below 20 nm. Topographic and antenna-enhanced photocurrent measurements reveal that the emission takes place at the location of highest local electric field indicating that the mechanism behind the emission is the radiative decay of excitons created via impact excitation

Chirality Changes in Carbon Nanotubes Studied with Near-Field Raman Spectroscopy

We report on the direct visualization of chirality changes in carbon nanotubes by mapping local changes in resonant RBM phonon frequencies with an optical resolution of 40 nm using near-field Raman spectroscopy. We observe the transition from semiconducting-to-metal and metal-to-metal chiralities at the single nanotube level. Our experimental findings, based on detecting changes in resonant RBM frequencies, are complemented by measuring changes in the G-band frequency and line shape. In addition, we observe increased Raman scattering due to local defects associated with the structural transition. From our results, we determine the spatial extent of the transition region to be Ltrans 40−100 nm

Trimerization of NaC2N3 to Na3C6N9 in the Solid

Sodium dicyanamide NaC2N3 was found to undergo two phase transitions. According to thermal analysis and temperature-dependent X-ray powder diffractometry, the transition of α-NaC2N3 (1a) to β-NaC2N3 (1b) occurs at 33°C and is displacive. 1a crystallizes in the monoclinic system, space group P21/n (no. 14), with a = 647.7(1), b = 1494.8(3), c = 357.25(7) pm, β = 93.496(1)°, and Z = 4. The structure was solved from powder diffraction data (Cu Kα1, T = 22°C) using direct methods and it was refined by the Rietveld method. The final agreement factors were wRp = 0.072, Rp = 0.053, and RF = 0.074. 1b crystallizes in the orthorhombic system, space group Pbnm (no. 62), with a = 650.15(5), b = 1495.1(2), c = 360.50(3) pm, and Z = 4. The structure was refined by the Rietveld method using the atomic coordinates of 1a as starting values (Mo Kα1, T = 150°C). The final agreement factors were wRp = 0.044, Rp = 0.034, RF = 0.140. The crystal structures of both polymorphs contain sheets of Na+ and N(CN)2- ions which are in 1a nearly and in 1b exactly coplanar. Above 340°C, 1b trimerizes in the solid to Na3C6N9 (2). 2 crystallizes in the monoclinic system, space group P21/n (no. 14), with a = 1104.82(1), b = 2338.06(3), c = 351.616(3) pm, β = 97.9132(9)°, and Z = 4. The structure was solved from synchrotron powder diffraction data (λ = 59.733 pm) using direct methods and it was refined by the Rietveld method. The final agreement factors were wRp = 0.080, Rp = 0.059, and RF = 0.080. The compound contains Na+ and the planar tricyanomelaminate C6N93-. The phase transition from 1b to 2 is reconstructive. It occurs in the solid-state without involvement of other phases or intermediates. The crystal structures of 1b and 2 indicate that there is no preorientation of the N(CN)2- in the solid before their trimerization to C6N93-