High-resolution infrared spectra of NCCN and NCCN

High-resolution spectra of ¹⁵N¹²C¹²C¹⁵N and ¹⁴N¹³C¹³C¹⁴N have been measured and analyzed from 200 to 3600 cm⁻¹. All the vibrational levels below 900 cm⁻¹ have been observed and characterized. The Fermi resonance between ν₂ and 2ν₄ has been studied and the resonance constant has been determined for several cases. Several Σ⁻ states have been directly observed for the first time for each isotopomer, the (0001111)0f, (0011111)0f, and (0002222)0f states. The pattern of the energy levels for clusters of l-type resonance coupled levels, such as 0001131,3, has been determined for cyanogen for the first time. Among other things this involved the determination of the vibrational l-type resonance constant, r₄₅. Many of the power series constants, α_i and x_ij, and higher order constants have been determined.     

New developments in millimeter wave spectroscopy

In the past few years millimeter and submillimeter wave spectroscopy has been the backbone for modern molecular line astronomy. The detection of unstable and high-temperature molecular species in the interstellar environment has stimulated the development of methods of detecting molecular ions, radicals and unstable molecules in the laboratory by means of millimeter wave technology. Some of the recent experimental advances as well as the developments which have occurred in the analysis of high resolution rotational and vibrational spectra with regard to understanding molecular dynamics will be discussed.     

Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

Far infrared spectra of solid molecular nitrogen

This paper reports the observation of the far infrared absorption spectrum of a single crystal of N₂, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm^–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed.     

The electronic absorption spectrum of the CNO free radical in the gas phase

A new band with heads at 796.3.3 and 7893.1 A has been found during the flash photolysis of 3-methyl-4-oximinoisoxazol-5(411)-one. By comparison with earlier work in a neon matrix. and on the basis of a partial rotational analysis, the band is assigned as the 0 0 band of the A²x⁺-X²11_i transition of the CNO free radical. Preliminary mlecular constant are given.     

Optical tuning of a tellurium cavity: optical modulation and bistability in the infrared region at room temperature

A new optical-optical modulator for the infrared region (4m < < 11m) is described. It is based on the tuning of the transmission of a plane parallel tellurium slab by free carriers created by multiphoton absorption of 10.6m and 5.3m radiation at room temperature. The operation of this device is described by a simple theory using the plane-wave approximation and the Drude-Zehner model. The assumptions of this theory were fulfilled by the experimental conditions, permitting a quantitative analysis of the registered modulations. Under certain working conditions pulse shortening (170 ns pulses of=5.3m were shortened by up to 20 ns) and fast switch-on of the device (switch-on time 2 ns) were observed. Moreover, the modulator exhibits limiter action and optical bistability which, for the first time, is observed in an intrinsic semiconductor device at room temperature.The substance of this paper was presented at the Conference on Ultrafast Phenomena in Spectroscopy at Reinhardsbrunn (GDR), in November 1980, and a preliminary account published in theProceedings of the meeting.     

Divergent Synthesis of Molecular Winch Prototypes

We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties.     

Star-Shaped Ruthenium Complexes as Prototypes of Molecular Gears

The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length.     

The Ground State Spectroscopic Parameters and Equilibrium Structure of PD3

Infrared spectra of PD₃ have been measured in the 20-320 cm⁻¹ range and in the region of the ν₂/ν₄ and ν₁/ν₃ fundamental bands near 750 and 1690 cm⁻¹, respectively, with a resolution of ca. 0.0025 cm⁻¹. Furthermore, submillimeter-wave spectra covering the J=4-3, 13-12, and 14-13 clusters in the vibrational ground state were recorded. The observed ΔJ=+1 rotational lines were augmented by about 5500 ground state combination differences formed from transitions belonging to the fundamental bands. Of these, 1300 involved perturbation-allowed lines with ΔK≠0. These data and observations taken from the literature were appropriately weighted and fitted to 14 ground state molecular constants. The A and B reductions of the rotational Hamiltonian were found to be equivalent. Improved effective ground state and equilibrium structures were determined for both PH₃ and PD₃; the equilibrium structures, r_e (PH)=141.1607(83) pm and α_e (HPH)=93.4184(95)° and r_e (PD)=141.1785(57) pm and α_e (DPD)=93.4252(68)°, are in good agreement.     

Millimeter-Wave Spectra of the CO Dimer: Three New States and Further Evidence of Distinct Isomers

The millimeter-wave spectrum of the normal isotope of the CO dimer, (¹²C¹⁶O)₂, has been systematically surveyed in the regions 75-105 and 131-174 GHz, with additional measurements covering the entire 60-176 GHz range. By combining these results and using the technique of combination differences based on previously known energy levels, 14 new rotational levels have been assigned and precisely (≈0.1 MHz) located. They belong to 3 completely new states, 1 with A⁺ symmetry and 2 with A⁻ symmetry. The position of the lowest energy A⁻ state results in a new and lower value for the effective tunneling splitting of the CO dimer, 3.73 cm⁻¹. The observation of dramatically different intensities for different bands supports the concept of two isomeric forms for (CO)₂, the ground state having a larger intermolecular separation (≈4.4 Å) with most likely a C-bonded configuration, and the low-lying (0.88 cm⁻¹) excited state having a smaller separation (≈4.0 Å) and an O-bonded geometry.