Divalent Metal Vinylphosphonate Layered Materials: Compositional Variability, Structural Peculiarities, Dehydration Behavior, and Photoluminescent Properties

A family of M-VP (M = Ni, Co, Cd, Mn, Zn, Fe, Cu, Pb; VP = vinylphosphonate) and M-PVP (M = Co, Cd; PVP = phenylvinylphosphonate) materials have been synthesized by hydrothermal methods and characterized by FTIR, elemental analysis, and thermogravimetric analysis (TGA). Their structures were determined either by single crystal X-ray crystallography or from laboratory X-ray powder diffraction data. The crystal structure of some M-VP and M-PVP materials is two-dimensional (2D) layered, with the organic groups (vinyl or phenylvinyl) protruding into the interlamellar space. However, the Pb-VP and Cu-VP materials show dramatically different structural features. The porous, three-dimensional (3D) structure of Pb-VP contains the Pb center in a pentagonal pyramid. A Cu-VP variant of the common 2D layered structure shows a very peculiar structure. The structure of the material is 2D with the layers based upon three crystallographically distinct Cu atoms; an octahedrally coordinated Cu2+ atom, a square planar Cu2+ atom and a Cu+ atom. The latter has an unusual co-ordination environment as it is 3-coordinated to two oxygen atoms with the third bond across the double bond of the vinyl group. Metal-coordinated water loss was studied by TGA and thermodiffractometry. The rehydration of the anhydrous phases to give the initial phase takes place rapidly for Cd-PVP but it takes several days for Co-PVP. The M-VP materials exhibit variable dehydration-rehydration behavior, with most of them losing crystallinity during the process.Proyecto nacional MAT2010-15175 (MICINN, España

A rotational investigation of the three isomeric forms of cyanoethynylbenzene (HCC-C6H4-CN): benchmarking experiments and calculations using the “Lego brick” approach

We report the study of three structural isomers of phenylpropiolonitrile (3-phenyl-2-propynenitrile, C6H5-C3N) containing an alkyne function and a cyano group, namely ortho-, meta-, and para-cyanoethynylbenzene (HCC-C6H4-CN). The pure rotational spectra of these species have been recorded at room temperature in the millimeter-wave domain using a chirped-pulse spectrometer (75-110 GHz) and a source-frequency modulation spectrometer (140-220 GHz). Assignments of transitions in the vibrational ground state and several vibrationally excited states were supported by quantum chemical calculations using the so-called “Lego brick” approach [A. Melli, F. Tonolo, V. Barone and C. Puzzarini, J. Phys. Chem. A, 2021, 125, 9904-9916]. From these assignments, accurate spectroscopic (rotational and centrifugal distortion) constants have been derived: for all species and all observed vibrational states, predicted rotational constants show relative accuracy better than 0.1%, and often of the order of 0.01%, compared to the experimental values. The present work hence further validates the use of the “Lego brick” approach for predicting spectroscopic constants with high precision

The SOLEIL view on sulfur rich oxides: The S2O bending mode nu(2) at 380 cm(-1) and its analysis using an Automated Spectral Assignment Procedure (ASAP)

The fundamental vibrational bending mode nu(2) of disulfur monoxide, S2O, and the associated hot band 2 nu(2) - nu(2) have been observed at high spectral resolution for the first time at the SOLEIL synchrotron facility using Fourier-transform far-infrared spectroscopy. This transient species has been produced in a radio-frequency discharge by flowing SO2 over elemental sulfur. The spectroscopic analysis has been performed using the newly developed Automated Spectral Assignment Procedure (ASAP) which has enabled the accurate determination of more than 3500 energy levels of the nu(2) = 1 and 2 vibrational states. The procedure provides a fast and convenient way to analyze large data sets in a straightforward manner, if one of the two vibrational states involved in the transition is accurately known from prior work. In addition to the high-resolution synchrotron study, pure rotational spectra of S2O in the nu(2) = 1 and 2 vibrational states were observed in the frequency range 250-500 GHz by absorption spectroscopy in a long-path absorption cell. From these combined measurements, extensive molecular parameter sets have been determined, including full sets of sextic and two octic centrifugal distortion terms. Highly accurate band centers (to better than 10(-5) cm(-1)) have been derived for both vibrational bands. (C) 2015 Elsevier Inc. All rights reserved

An ASAP treatment of vibrationally excited S2O: The v(3) mode and the v(3) + v(2) - v(2) hot band

The fundamental S-S stretching mode v(3) of disulfur monoxide, S2O, located at 679 cm(-1), has been investigated using Fourier-transform far-infrared spectroscopy at the SOLEIL synchrotron facility. A spectroscopic analysis has been performed using an Automated Spectral Assignment Procedure (ASAP) which permits accurate determination of more than 2000 energy levels from v3. In addition, the v(3) + v(2)-v(2) hot band was observed for the first time and some 500 corresponding energy levels were assigned. The high-resolution synchrotron study was complemented with pure rotational spectra of S2O in the (v(1), v(2), v(3)) = (0, 0,1) vibrational state observed in the frequency range from 250 to 280 GHz using a long-path absorption cell. From these combined measurements, extensive molecular parameter sets have been determined and precise band centers have been derived for both vibrational bands. (C) 2015 Elsevier Inc. All rights reserved

Far-infrared laboratory spectroscopy of aminoacetonitrile and first interstellar detection of its vibrationally excited transitions

Context. Aminoacetonitrile, a molecule detected in the interstellar medium only toward the star-forming region Sagittarius B2 (Sgr B2), is considered an important prebiotic species; in particular, it is a possible precursor of the simplest amino acid glycine. To date, observations have been limited to ground state emission lines, whereas transitions from within vibrationally excited states remained undetected. Aims. We wanted to accurately determine the energies of the low-lying vibrational states of aminoacetonitrile, which are expected to be populated in Sgr B2(N1), the main hot core of Sgr B2(N). This step is fundamental in order to properly evaluate the vibration-rotation partition function of aminoacetonitrile as well as the line strengths of the rotational transitions of its vibrationally excited states. This is necessary to derive accurate column densities and secure the identification of these transitions in astronomical spectra. Methods. The far-infrared ro-vibrational spectrum of aminoacetonitrile has been recorded in absorption against a synchrotron source of continuum emission. Three bands, corresponding to the lowest vibrational modes of aminoacetonitrile, were observed in the frequency region below 500 cm-1. The combined analysis of ro-vibrational and pure rotational data allowed us to prepare new spectral line catalogs for all the states under investigation. We used the imaging spectral line survey ReMoCA performed with ALMA to search for vibrationally excited aminoacetonitrile toward Sgr B2(N1). The astronomical spectra were analyzed under the local thermodynamic equilibrium (LTE) approximation. Results. Almost 11 000 lines have been assigned during the analysis of the laboratory spectrum of aminoacetonitrile, thanks to which the vibrational energies of the v11 = 1, v18 = 1, and v17 = 1 states have been determined. The whole dataset, which includes high J and Ka transitions, is well reproduced within the experimental accuracy. Reliable spectral predictions of pure rotational lines can now be produced up to the THz region. On the basis of these spectroscopic predictions, we report the interstellar detection of aminoacetonitrile in its v11 = 1 and v18 = 1 vibrational states toward Sgr B2(N1) in addition to emission from its vibrational ground state. The intensities of the identified v11 = 1 and v18 = 1 lines are consistent with the detected v = 0 lines under LTE at a temperature of 200 K for an aminoacetonitrile column density of 1.1 × 1017 cm-2. Conclusions. This work shows the strong interplay between laboratory spectroscopy exploiting (sub)millimeter and synchrotron-based far-infrared techniques, and observational spectral surveys to detect complex organic molecules in space and quantify their abundances

Far-infrared laboratory spectroscopy of aminoacetonitrile and first interstellar detection of its vibrationally excited transitions

Context. Aminoacetonitrile, a molecule detected in the interstellar medium only toward the star-forming region Sagittarius B2 (Sgr B2), is considered an important prebiotic species; in particular, it is a possible precursor of the simplest amino acid glycine. To date, observations have been limited to ground state emission lines, whereas transitions from within vibrationally excited states remained undetected.Aims. We wanted to accurately determine the energies of the low-lying vibrational states of aminoacetonitrile, which are expected to be populated in Sgr B2(N1), the main hot core of Sgr B2(N). This step is fundamental in order to properly evaluate the vibration-rotation partition function of aminoacetonitrile as well as the line strengths of the rotational transitions of its vibrationally excited states. This is necessary to derive accurate column densities and secure the identification of these transitions in astronomical spectra.Methods. The far-infrared ro-vibrational spectrum of aminoacetonitrile has been recorded in absorption against a synchrotron source of continuum emission. Three bands, corresponding to the lowest vibrational modes of aminoacetonitrile, were observed in the frequency region below 500 cm(-1). The combined analysis of ro-vibrational and pure rotational data allowed us to prepare new spectral line catalogs for all the states under investigation. We used the imaging spectral line survey ReMoCA performed with ALMA to search for vibrationally excited aminoacetonitrile toward Sgr B2(N1). The astronomical spectra were analyzed under the local thermodynamic equilibrium (LTE) approximation.Results. Almost 11 000 lines have been assigned during the analysis of the laboratory spectrum of aminoacetonitrile, thanks to which the vibrational energies of the v(11)=1, v(18)=1, and v(17)=1 states have been determined. The whole dataset, which includes high J and K-a transitions, is well reproduced within the experimental accuracy. Reliable spectral predictions of pure rotational lines can now be produced up to the THz region. On the basis of these spectroscopic predictions, we report the interstellar detection of aminoacetonitrile in its v(11)=1 and v(18)=1 vibrational states toward Sgr B2(N1) in addition to emission from its vibrational ground state. The intensities of the identified v(11)=1 and v(18)=1 lines are consistent with the detected v=0 lines under LTE at a temperature of 200 K for an aminoacetonitrile column density of 1.1x10(17) cm(-2).Conclusions. This work shows the strong interplay between laboratory spectroscopy exploiting (sub)millimeter and synchrotron-based far-infrared techniques, and observational spectral surveys to detect complex organic molecules in space and quantify their abundances

Submillimeter spectroscopy and astronomical searches of vinyl mercaptan, C2H3SH

Context. New laboratory investigations of the rotational spectrum of postulated astronomical species are essential to support the assignment and analysis of current astronomical surveys. In particular, considerable interest surrounds sulfur analogs of oxygen-containing interstellar molecules and their isomers. Aims. To enable reliable interstellar searches of vinyl mercaptan, the sulfur-containing analog to the astronomical species vinyl alcohol, we investigated its pure rotational spectrum at millimeter wavelengths. Methods. We extended the pure rotational investigation of the two isomers syn and anti vinyl mercaptan to the millimeter domain using a frequency-multiplication spectrometer. The species were produced by a radiofrequency discharge in 1,2-ethanedithiol. Additional transitions were remeasured in the centimeter band using Fourier-transform microwave spectroscopy to better determine rest frequencies of transitions with low-J and low-K-a values. Experimental investigations were supported by quantum chemical calculations on the energetics of both the [C-2, H-4, S] and [C-2, H-4, O] isomeric families. Interstellar searches for both syn and anti vinyl mercaptan as well as vinyl alcohol were performed in the EMoCA spectral line survey carried out toward Sgr B2(N2) with ALMA. Results. Highly accurate experimental frequencies (to better than 100 kHz accuracy) for both syn and anti isomers of vinyl mercaptan are measured up to 250 GHz; these deviate considerably from predictions based on extrapolation of previous microwave measurements. Reliable frequency predictions of the astronomically most interesting millimeter-wave lines for these two species can now be derived from the best-fit spectroscopic constants. From the energetic investigations, the four lowest singlet isomers of the [C-2, H-4, S] family are calculated to be nearly isoenergetic, which makes this family a fairly unique test bed for assessing possible reaction pathways. Upper limits for the column density of syn and anti vinyl mercaptan are derived toward the extremely molecule-rich star-forming region Sgr B2(N2) enabling comparison with selected complex organic molecules