The organic molecular porous material 1 obtained by recrystallization of cucurbit[6]uril (CB[6]) from HCl shows a high CO(2) sorption capacity at 298 K, 1 bar. Most interestingly, 1 showed the highest selectivity of CO(2) over CO among the known porous materials so far. The remarkable selectivity of CO(2) may be attributed to the exceptionally high enthalpy of adsorption (33.0 kJ/mol). X-ray crystal structure analysis of CO(2) adsorbed 1 revealed three independent CO(2) sorption sites: two in the 1D channels (A and B) and one in the molecular cavities (C). The CO(2) molecules adsorbed at sorption site A near the wall of the 1D channels interact with 1 through hydrogen bonding and at the same time interact with those at site B mainly through quadrupole-quadrupole interaction in a T-shaped arrangement. Interestingly, two CO(2) molecules are included in the CB[6] cavity (site C), interacting not only with the carbonyl groups of CB[6] but also with each other in a slipped-parallel geometry. The exceptionally selective CO(2) sorption properties of 1 may find useful applications in the pressure swing adsorption (PSA) process for CO(2) separation not only in the steel industry but also in other industries such as natural gas mining.
We report a dynamically tunable reflectarray metasurface that continuously modulates the phase of reflected light in the near-infrared wavelength range under active electrical control of the phase transition from semiconducting to semimetallic states. We integrate a vanadium dioxide (VO 2) active layer into the dielectric gap of antenna elements in a reflectarray metasurface, which undergoes an insulator-to-metal transition upon resistive heating of the metallic patch antenna. The induced phase transition in the VO 2 film strongly perturbs the magnetic dipole resonance supported by the metasurface. By carefully controlling the volume fractions of coexisting metallic and dielectric regions of the VO 2 film, we observe a continuous shift of the phase of the reflected light, with a maximal achievable phase shift as high as 250°. We also observe a reflectance modulation of 23.5% as well as a spectral shift of the resonance position by 175 nm. The metasurface phase modulation is fairly broadband, yielding large phase shifts at multiple operation wavelengths.
Cucurbituril‐based organic molecular porous materials with 1D channels filled with water–acid arrays were synthesized. The isostructural materials showed different proton conductivity depending on the nature and number of acid molecules present in the channels. The highly anisotropic conduction behavior of the materials was studied by single‐crystal conductivity measurements.
The porphyrin boxes (PB-1 and PB-2), which are rationally designed porous organic cages with a large cavity using well-defined and rigid 3-connected triangular and 4-connected square shaped building units are reported. PB-1 has a cavity as large as 1.95 nm in diameter and shows high chemical stability in a broad pH range (4.8 to 13) in aqueous media. The crystalline nature as well as cavity structure of the shape-persistent organic cage crystals were intact even after complete removal of guest molecules, leading to one of the highest surface areas (1370 m(2) g(-1)) among the known porous organic molecular solids. The size of the cavities and windows of the porous organic cages can be modulated using different sized building units while maintaining the topology of the cages, as illustrated with PB-2. Interestingly, PB-2 crystals showed unusual N2 sorption isotherms as well as high selectivity for CO2 over N2 and CH4 (201 and 47.9, respectively at 273 K at 1 bar).
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