Reversible Encapsulation of Xenon and CH₂Cl₂ in a Solid‐State Molecular Organometallic Framework (Guest@SMOM)

Abstract

Reversible encapsulation of CH2Cl2 or Xe in a non‐porous solid‐state molecular organometallic framework of [Rh(Cy2PCH2PCy2)(NBD)][BArF4] occurs in single‐crystal to single‐crystal transformations. These processes are probed by solid‐state NMR spectroscopy, including 129Xe SSNMR. Non‐covalent interactions with the ‐CF3 groups, and hydrophobic channels formed, of [BArF4]− anions are shown to be important, and thus have similarity to the transport of substrates and products to and from the active site in metalloenzymes.

Selectivity of Rh⋅⋅⋅H−C Binding in a σ‐Alkane Complex Controlled by the Secondary Microenvironment in the Solid State

“…Such remarkable reactivity and stability in the solid state results from the periodic arrangement of [BAr F 4 ] − anions. These form an encapsulating, approximately octahedral ( O h ) microenvironment around the cationic σ‐complex (Figure 1 D), [11, 14] which provides stabilizing noncovalent interactions and substrate‐accessible hydrophobic channels [17] . We now report that the regioselectivity of alkane binding can be controlled by subtle changes to this periodic microenvironment, which are encoded by the cationic precursor metal–ligand fragment.…”

A Series of Crystallographically Characterized Linear and Branched σ-Alkane Complexes of Rhodium: From Propane to 3-Methylpentane

“…This crystalline 27 nanoreactor 28 environment allows for long-range order to be retained, local coordinate flexibility at the reactive site, and hydrophobic pathways through the lattice from the CF 3 groups. 29 The retention of crystallinity also allows for detailed characterization by single-crystal X-ray diffraction and solid-state NMR spectroscopy (SSNMR).…”

Static and Dynamic Adsorptions of Water Vapor by Cyclic [Zr36] Clusters: Implications for Atmospheric Water Capture Using Molecular Solids

“…We note that ZF-3h is a rare case of molecular solids with the "permanent" porosity proven by gas sorption data. [13][14][15][16][17][18][19][20][21] One of the motivations behind this study was to investigate molecular solids toward water vapor adsorption which has numerous practical implications. Especially, the adsorptive removal or harvest of atmospheric water vapor is a topic of increasing significance, [33][34][35][36][37] and several MOFs are being studied intensively as adsorbents for the production of fresh water in arid regions, [38][39] for indoor moisture BULLETIN OF THE KOREAN CHEMICAL SOCIETY control 40 or for adsorption heat pump systems.…”

“…A survey of recent literature reveals that the most common forms of inorganic molecular solids showing gas adsorption behavior are coordination cages, [9][10][11][12] metallacycles, [13][14][15][16] or simple complexes self-assembled into open structures. [17][18][19][20][21] Further development in this area may be related to an outlook that porosity can be linked to molecular materials even without a crystal lattice, such as in liquid or glass state. [22][23][24][25][26][27] Note that until now discussions of functional molecular solids have been based on the assumption of crystal-like molecular packing either on the surface or in bulk.…”