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

Carbon dioxide (CO) is widespread in astrochemically relevant environments, often coexisting with water (HO) ices and thus triggering a great interest regarding the possible formation of their adducts under various thermodynamic conditions. Amongst them, solid carbonic acid (HCO) 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).

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.

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).

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.

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.

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

The ambient temperature photoinduced polymerization of compressed ( < 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.