Exploring High-Pressure Polymorphism in Carbonic Acid through Direct Synthesis from Carbon Dioxide Clathrate Hydrate.

Carbon dioxide (CO2) is widespread in astrochemically relevant environments, often coexisting with water (H2O) ices and thus triggering a great interest regarding the possible formation of their adducts under various thermodynamic conditions. Amongst them, solid carbonic acid (H2CO3) remains elusive, yet being widely studied. Synthetic routes followed for its production have always been characterised by drastic irradiation on solid ice mixtures or complex procedures on fluid samples (such as laser heating at moderate to high pressures). Here we report about a simpler yet effective synthetic route to obtain two diverse carbonic acid crystal structures from the fast, cold compression of pristine clathrate hydrate samples. The two distinct polymorphs we obtained, differing in the water content, have been deeply characterised via spectroscopic and structural techniques to assess their composition and their astonishing pressure stability, checked up to half a megabar, also highlighting the complex correlations between them so to compile a detailed phase diagram of this system. These results may have a profound impact on the prediction and modelisation of the complex chemistry which characterises many icy bodies of our Solar System.

High-pressure structure and reactivity of crystalline bibenzyl: Insights and prospects for the synthesis of functional double-core carbon nanothreads.

The high-pressure synthesis of double-core nanothreads derived from pseudo-stilbene crystals represents a captivating approach to isolate within the thread chromophores or functional groups without altering its mechanical properties. These entities can be effectively utilized to finely tune optical properties or as preferential sites for functionalization. Bibenzyl, being isostructural with other members of this class, represents the ideal system for building co-crystals from which we can synthesize double-core nanothreads wherein bridging chromophores, such as the azo or ethylene moieties, are embedded in the desired concentration within a fully saturated environment. To achieve this, a critical step is the preliminary characterization of the high-pressure behavior of crystalline bibenzyl. We report here an accurate investigation performed through state-of-the-art spectroscopic techniques, Raman and Fourier transform infrared spectroscopy, and x-ray diffraction up to 40 GPa. Our findings reveal a strongly anisotropic compression of the crystal, which determines, at pressures between 1 and 2 GPa, consistent modifications of the vibrational spectrum, possibly related to a torsional distortion of the molecules. A phase transition is detected between 9 and 10 GPa, leading to a high pressure phase where, above 24 GPa, the nanothread formation is observed. However, the observed reaction was limited in extent and required significantly higher pressures in comparison to other members of the pseudo-stilbene family. This comprehensive study is imperative in laying the foundation for future endeavors, aiming to synthesize double-core nanothreads from pseudo-stilbene crystals, and provides crucial insights into the high-pressure behavior and phase transitions of crystalline bibenzyl.

High pressure decomposition of a sandwich compound.

While it is widely recognized that purely organic molecular systems with multiple bonds undergo chemical condensation at sufficiently high pressures (from tenths to tens of GPa), the fate of organometallics at extreme conditions remains largely underexplored. We have investigated the high pressure (up to 41 GPa) chemical transformations in a simple molecular system known as nickelocene, (C5H5)2Ni, which serves as a representative example of a class of organometallics called sandwich compounds. Nickelocene decomposed above 13 GPa, at room temperature, while lower pressure thresholds have been observed at higher temperatures (295-573 K). The products were identified as nanocomposite materials, primarily composed of disordered, nickel-rich nanoparticles segregated within an extended, amorphous matrix of hydrogenated carbon (a-C:H). The investigation was conducted by means of diamond anvil cells in combination with optical spectroscopies and microscopy, synchrotron x-ray absorption spectroscopy and diffraction, as well as transmission electron microscopy. Our findings have the potential to stimulate further research into the high-pressure chemical reactivity of organometallics and open up new synthesis routes for the production of metal-based nanoparticles, which find a wide range of applications.

Towards custom built double core carbon nanothreads using stilbene and pseudo-stilbene type systems.

Until recently, saturated carbon nanothreads were the missing tile in the world of low-dimension carbon nanomaterials. These one-dimensional fully saturated polymers possess superior mechanical properties by combining high tensile strength with flexibility and resilience. They can be obtained by compressing aromatic and heteroaromatic crystals above 15 GPa exploiting the anisotropic stress that can be achieved by the diamond anvil cell technique. Recently, double-core nanothreads were synthesized by compressing azobenzene crystals, achieving the remarkable result of preserving the azo group as a linker of the resulting double thread. Herein, we demonstrate the generality of these findings through the synthesis of double carbon nanothreads from trans stilbene and azobenzene-stilbene mixed crystals. Employment of Fourier transform infrared spectroscopy and synchrotron X-ray diffraction enabled a comprehensive characterization of the reactivity identifying threshold conditions, kinetics and structure-reaction relationship. In particular, the reaction is anticipated by a phase transition characterized by a sudden increase of the monoclinic angle and a collapse along the b axis direction. Large bidimensional crystalline areas extending several tens of nanometers are evidenced by transmission electron microscopy also confirming the monoclinic unit cell derived from X-ray diffraction data in which threads possessing the polymer 1 structure, as suggested by density functional theory calculations, are packed. The most exciting result of this study is the demonstration of viable synthesis of double nanothreads where the number and the nature of chromophoric groups linking the threads can be tuned by preparing starting crystals of desired composition, thanks to the isomorphism typical of the pseudo-stilbene molecules. This is extremely important in tailoring nanothreads with tunable optical properties and an adjustable band gap, also exploiting the possibility of introducing substituents in the phenyl groups.

Synthesis of double core chromophore-functionalized nanothreads by compressing azobenzene in a diamond anvil cell.

Carbon nanothreads are likely the most attracting new materials produced under high pressure conditions. Their synthesis is achieved by compressing crystals of different small aromatic molecules, while also exploiting the applied anisotropic stress to favor nontopochemical paths. The threads are nanometric hollow structures of saturated carbon atoms, reminiscent of the starting aromatic molecule, gathered in micron sized bundles. The examples collected so far suggest that their formation can be a general phenomenon, thus enabling the design of functionalities and properties by suitably choosing the starting monomer on the basis of its chemical properties and crystal arrangement. The presence of heteroatoms or unsaturation within the thread is appealing for improving the processability and tuning the electronic properties. Suitable simple chromophores can fulfill these requirements and their controlled insertion along the thread would represent a considerable step forward in tailoring the optical and electronic properties of these mechanically extraordinary materials. Here, we report the synthesis and extensive characterization of double core nanothreads linked by azo groups. This is achieved by compressing azobenzene in a diamond anvil cell, the archetype of a wide class of dyes, and represents a fundamental step in the realization of nanothreads with tailored photochemical and photophysical properties.

Accessing the Activation Mechanisms of Ethylene Photo-Polymerization under Pressure by Transient Infrared Absorption Spectroscopy.

The ambient temperature photoinduced polymerization of compressed (P < 1 GPa) fluid ethylene was characterized by transient infrared absorption spectroscopy with a resolution of few nanoseconds, 3 orders of magnitude higher than previously reported. The reaction has been studied under both one- and two-photon excitation evidencing in the latter case its occurrence only in the presence of different transition metal oxides. Their photocatalytic activity is ascribed to the stabilization of the excited biradicals through electron density exchange between the d orbitals of the metal and the π antibonding orbitals of ethylene which lengthens the lifetime of the biradicals. In both one- and two-photon activation cases the polymerization is characterized by an initial step distinguished by a molecularity of 0.15 ± 0.02 identified as the activation step of the reaction lasting, in the one-photon excitation case, a few hundreds of nanoseconds. Using pulsed excitation the reaction evolves toward a free radical polymerization only under one-photon excitation whereas the critical concentration of radicals required to propagate the reaction is never achieved in the two-photon excitation case. Comparison with continuous wave excitation unambiguously identifies in the average power released to the sample the key factor to drive quantitatively and qualitatively the polymerization.