Search Results (3)

The separation of chlorobenzene (CB) and chlorocyclohexane (CCH) using traditional industrial separation technologies (distillation, fractionation, and rectification) is a great challenge due to their close boiling points. Here, we report an innovative method for the separation of the mixture of CB and CCH by nonporous adaptive crystals (NACs) of perethylated pillar[6]arene (EtP6). NACs of EtP6 (EtP6α) can selectively adsorb CCH vapor from the vapor mixture of CB and CCH (v:v = 1:1) with a purity of 99.5%. Furthermore, EtP6α can be recycled for five times without a significant loss of performance. Full article

The selective adsorption and separation of benzene from structurally similar six-membered hydrocarbons and fluorocarbons remain a significant challenge due to their comparable physical properties. In this study, we investigated the molecular recognition and separation properties of a perfluorinated triketonate Cu(II) complex (1) as a Nonporous Adaptive Crystal (NAC). In addition to the previously reported benzene (2)-encapsulated crystal of 1•(2)₃, we report here the crystal structures of guest-free 1 and cyclohexene (3)-encapsulated 1•(O)₂•3, where (O)₂ represents two water molecules. Single-crystal analysis demonstrated that 1 selectively encapsulates 2 while excluding other hydrocarbons, including 3, cyclohexane (4), trifluorobenzene (5), and hexafluorobenzene (6). Gas adsorption experiments confirmed this high affinity for 2, as reflected in its preferential adsorption behavior in mixed solvent and vapor environments. The molecular selectivity of 1 was attributed to strong π-hole···π and metal···π interactions, which favor electron-rich aromatic guests. Additionally, crystallization experiments in competitive solvent systems consistently led to the formation of 1•(2)₃, reinforcing the high selectivity of 1 for 2. These findings highlight the unique molecular recognition capabilities of NACs, providing valuable insights into the rational design of advanced molecular separation materials for industrial applications involving aromatic hydrocarbons. Hirshfeld surface analysis revealed that the contribution of F···F interactions to crystal packing decreased upon guest recognition (48.8% in 1, 34.2% in 1•(O)₂•3, and 22.2% in 1•(2)₃), while the contribution of F···H/H···F interactions increased (8.6% in 1, 22.2% in 1•(O)₂•3, and 35.4% in 1•(2)₃). Regarding Cu interactions, the self-assembled columnar structure of 1 results in close contacts at the coordination sites, including Cu···Cu (0.1%), Cu···O (0.7%), and Cu···C (1.3%). However, in the guest-incorporated structures 1•(O)₂•3 and 1•(2)₃, the Cu···Cu contribution disappears; instead, 1•(O)₂•3 exhibits a significant increase in Cu···O interactions (1.2%), corresponding to water coordination, while 1•(2)₃ shows an increase in Cu···C interactions (1.5%), indicative of the metal···π interactions of benzene. Full article

The three isomers of the tetraoxa[4]arene derivative, C₂₄H₁₆O₄, which consist of two m-phenylenes and two phenylenes (meta 1, para 2, ortho 3), represent not only intriguing fundamental structures that induce molecular recognition toward non-porous adaptive crystals, but also attractive candidates for crystallographic polymorphism. In this study, we crystallized isomers 2 and 3, in comparison to isomer 1, in order to understand their stable orientations and the corresponding intermolecular interactions in the crystalline state. For example, m-phenylene derivative 1 exhibits polymorphism with both prismatic and block-shaped crystals. Therefore, we prepared p-phenylene derivative 2 and o-phenylene derivative 3, and their structures were fully characterized by SC-XRD, revealing two polymorphs of derivative 2, namely prismatic crystal 2-I and block-shaped crystal 2-II, along with changes to the crystal lattice parameters (2-Ia, 2-Ib, and 2-Ic) based on temperature dependence. In all of its crystal forms, derivative 2 adopts an O-shaped planar structure, where the p-phenylene units face each other. This suggests that the packing mode during the early stages of crystallization, rather than due to any remarkable changes in the molecular structure, directly affects the bulk crystal morphology. On the other hand, derivative 3 adopts a U-shaped vent structure and, to the best of our knowledge, does not form polymorphs. The Platon and Hirshfeld surface analyses indicated that the contributions to the crystal packing were C···C (av. 37.3% for 2-Ia, av. 38.2% for 2-II, and 18.7% for 3), C···H/H···C (av. 37.3% for 2-Ia, av. 38.2% for 2-II, and 18.7% for 3), and O···H/H···O (av. 17.8% for 2-Ia, av. 19.6% for 2-II, and 19.4% for 3), highlighting significant intermolecular CH···π interactions and pseudo-hydrogen bonding forms for derivative 2 and π···π interactions for derivative 3. Full article