Selective CO2 uptake mimics dissolution in extremely fluorinated non-porous crystalline supplies

Materials

All reagents had been bought from Aldrich or Alfa Aesar. High-purity carbon dioxide and methane gases had been equipped by BOC and used as acquired. CO₂ sorption measurements had been made utilizing an Intelligent Gravimetric Analyser mannequin 003 equipped by Hiden Isochema Ltd. Elemental analyses had been carried out by the Elemental Analysis Service within the Department of Chemistry on the University of Sheffield.

Synthesis

A homologous sequence of isoreticular AgCPs [Ag₄(CO₂(CF₂)_mCF₃)₄(TMP)₃(ROH)₂]∙xCH₂Cl₂ (m = 2 (1-MeOH), 3 (2-EtOH), 4 (3-EtOH), 5 (4-MeOH) and 6 (5-MeOH); ROH = methanol or ethanol; x = 0 or 1 (5-MeOH solely); Extended Data Table 1) has been synthesized as giant colourless needle crystals by a gradual liquid diffusion course of at 278 Ok. Alcohol-free AgCPs [Ag₄(CO₂(CF₂)_mCF₃)₄(TMP)₃] (m = 2 (1), 3 (2), 4 (3), 5 (4) and 6 (5)) had been obtained upon gentle heating of compounds 1-ROH–5-ROH. These supplies had been ready following the same process to these reported in ref. ¹⁷.

Synthesis of [Ag₄(O₂C(CF₂)₂CF₃)₄(TMP)₃(MeOH)₂] (1-MeOH)

Silver(I) heptafluorobutanoate (96 mg, 0.30 mmol) was dissolved in methanol (1.5 ml) and thoroughly layered on an answer of TMP (30 mg, 0.220 mmol) in dichloromethane (DCM) answer (1 ml). Diffusion between layers at 5 °C afforded a combination of colourless needle and plate crystals. Separation of the needle crystals below the microscope resulted in 81% yield inside 3 days. Calc.: C, 28.72; H, 2.52; N, 4.78%; discovered C, 28.59; H, 2.14; N, 4.91%.

Synthesis of [Ag₄(O₂C(CF₂)₂CF₃)₄(TMP)₃] (1)

Compound 1 (in polymorphic kind 1_A^HT) is finest synthesized by launch of alcohol from 1-MeOH. 1-MeOH (100 mg, 0.0569 mmol) was positioned in an open vial at room temperature for every week to allow MeOH vapour launch. White crystals of 1_A^HT fashioned quantitatively. Calc.: C, 28.38; H, 2.12; N, 4.96%. Found: C, 28.17; H, 2.23; N, 4.72%. The part purity and id of the polymorph was confirmed by Rietveld refinement of powder X-ray diffraction knowledge.

Synthesis of [Ag(O₂C(CF₂)₃CF₃)]

Silver(I) carbonate (372 mg, 1.35 mmol) was partially dissolved in 25 ml of methanol. Perfluoropentanoic acid (0.42 ml, 2.7 mmol) was added dropwise with a syringe to the methanol answer. The response combination was stirred till your entire methanol was evaporated, affording 902 mg of white powder in 90% yield Calc.: C, 18.04; H, 0; N, 0%. Found: 18.34; H, 0; N, 0.21%.

Synthesis of [Ag₄(O₂C(CF₂)₃CF₃)₄(TMP)₃(EtOH)₂] (2-EtOH)

Silver(I) nonafluoropentanoate (100 mg, 0.29 mmol) was dissolved in ethanol (1.5 ml) and thoroughly layered on an answer of TMP (26 mg, 0.19 mmol) in DCM answer (1 ml). Diffusion between layers at 5 °C afforded colourless needles and plate crystals inside 3 days. The presence of CP [Ag₄(O₂C(CF₂)₃CF₃)₄(TMP)₂]_n as an impurity was confirmed by Rietveld refinement of powder X-ray diffraction knowledge. Separation between colourless needles and plates enabled purification of 2-EtOH.

Synthesis of [Ag₄(O₂C(CF₂)₃CF₃)₄(TMP)₃] (2)

Compound 2 is finest synthesized by the discharge of ethanol from 2-EtOH CP. Crystals of 2-EtOH (100 mg, 0.0503 mmol) that had been beforehand chosen below the microscope had been positioned in an open vial in an oven at 60 °C for 3 h to allow ethanol vapour launch. White crystals of 2 fashioned quantitatively. Calc.: C, 27.93; H, 1.92; N, 4.44%. Found: C, 28.17; H, 2.23; N, 4.72%.

Synthesis of [Ag(O₂C(CF₂)₄CF₃)]

Silver(I) carbonate (328 mg, 1.2 mmol) was partially dissolved in 25 ml of methanol. Perfluorohexanoic acid (0.42 ml, 2.37 mmol) was added dropwise with a syringe to the methanol answer. The response combination was stirred till all methanol was evaporated, affording 847 mg of white powder in 75% yield Calc.: C, 17.10; H, 0; N, 0%. Found: C, 17.05; H, 0; N, 0.24 %.

Synthesis of [Ag₄(O₂C(CF₂)₄CF₃)₄(TMP)₃(EtOH)₂] (3-EtOH)

Silver(I) undecafluorohexanoate (100 mg, 0.24 mmol) was dissolved in ethanol (1.5 ml) and thoroughly layered on an answer of TMP (24 mg, 0.18 mmol) in DCM answer (1 ml). Diffusion between layers at 5 °C afforded colourless needles and plates. Separation of the needle crystals below the microscope resulted in 72% yield inside 3 days. Calc.: C, 28.53; H, 2.22; N, 3.85%. Found: C, 28.04; H, 1.89; N, 3.71 %.

Synthesis of [Ag₄(O₂C(CF₂)₄CF₃)₄(TMP)₃] (3)

Compound 3 is finest synthesized by launch of the alcohol molecule from 3-EtOH CP. Crystals of 3-EtOH (100 mg, 0.0457 mmol) had been positioned in an open vial in an oven for 3 h at 60 °C to allow EtOH vapour launch. White crystals of 3 fashioned quantitatively. Calc.: C, 27.56; H, 1.73; N, 4.02%. Found: C, 27.65; H, 1.42; N, 3.91 %.

Synthesis of [Ag(O₂C(CF₂)₅CF₃)]

Silver(I) carbonate (292 mg, 1.1 mmol) was partially dissolved in 25 ml of methanol. Perfluoroheptanoic acid (771 mg, 2.12 mmol) was added and stirred till all methanol was evaporated, affording 843 mg of white powder in 84% yield. Calc.: C, 17.83; H, 0; N, 0%. Found: C, 17.71; H, 0; N, 0%.

Synthesis of [Ag₄(O₂C(CF₂)₅CF₃)₄(TMP)₃(MeOH)₂] (4-MeOH)

Silver(I) tridecafluoroheptanoate (100 mg, 0.21 mmol) was dissolved in methanol (1.5 ml) and thoroughly layered on an answer of TMP (21 mg, 0.16 mmol) in DCM answer (1 ml). Diffusion between layers at 5 °C afforded colourless needles and plates. Separation of the needle crystals below the microscope resulted in 86% yield inside 3 days. Calc.: C, 27.52; H, 1.88; N, 3.57%. Found: C, 27.77; H, 2.04; N, 3.75%.

Synthesis of [Ag₄(O₂C(CF₂)₄CF₃)₄(TMP)₃] (4)

Compound 4 is finest synthesized by the discharge of the methanol molecules from 4-MeOH. Crystals of 4-MeOH (100 mg, 0.0436 mmol) had been positioned in an open vial in an oven for 3 h at 60 °C to allow MeOH vapour launch. White crystals of 4 fashioned quantitatively. Calc.: C, 27.25; H, 1.58; N, 3.67%. Found: C, 27.27; H, 1.16; N, 3.58 %.

Synthesis of [Ag(O₂C(CF₂)₆CF₃)]

Silver(I) carbonate (264 mg, 0.96 mmol) was partially dissolved in 25 ml of methanol. Perfluorooctanoic acid (790 mg, 1.91 mmol) was added and stirred till all methanol was evaporated, affording 962 mg of white powder in 96% yield. Calc.: C, 18.42; H, 0; N, 0%. Found: C, 18.16; H, 0; N, 0.43%.

Synthesis of [Ag₄(O₂C(CF₂)₆CF₃)₄(TMP)₃(MeOH)₂]·CH₂Cl₂ (5-MeOH)

Silver(I) perfluorooctanoate (100 mg, 0.19 mmol) was dissolved in methanol (1.5 ml) and thoroughly layered on an answer of TMP (18 mg, 0.13 mmol) in DCM answer (1 ml). Diffusion between layers at 5 °C afforded colourless needles and plates. Separation of the needle crystals below the microscope resulted in 86% yield inside 3 days. Calc.: C, 26.83; H, 1.75; N, 3.18%. Found: C, 26.79; H, 1.29; N, 3.02 %

Synthesis of [Ag₄(O₂C(CF₂)₄CF₃)₄(TMP)₃] (5)

Compound 5 is finest synthesized by the discharge of ethanol molecules from 5-MeOH. Crystals of 5-MeOH (100 mg, 0.0386 mmol) had been positioned in an open vial in an oven for 3 h at 60 °C to allow MeOH vapour launch. White crystals of 5 fashioned quantitatively. Calc.: C, 26.99; H, 1.46; N, 3.37%. Found: C, 26.79; H, 1.29; N, 3.23 %.

SCXRD

Crystal construction dedication and refinement

X-ray knowledge had been processed and lowered utilizing APEX2 or CrysAlisPro applications and corrected for absorption utilizing empirical strategies (SADABS⁵⁴ or Scale3 Abspack) based mostly upon symmetry-equivalent reflections mixed with measurements at totally different azimuthal angles. All crystal buildings had been solved and refined towards all F² values utilizing OLEX2⁵⁵ and/or SHELX⁵⁶. A abstract of the info assortment and construction refinement data is supplied in Supplementary Tables 1–11. Non-hydrogen atoms had been refined anisotropically the place potential, whereas hydrogen atoms had been positioned in calculated positions, refined utilizing idealized geometries (using mannequin) and assigned mounted isotropic displacement parameters. In most of the construction determinations, fluoroalkyl chains are described as disordered over two orientations with carbon and fluorine atoms modelled utilizing isotropic displacement parameters. Distance restraints (SAME, SADI and DFIX instructions in SHELX) had been utilized to C–F and C–C bonds. Atomic displacement parameters of atoms within the perfluoroalkyl chains had been restrained utilizing a rigid-body method by making use of SHELX RIGU instructions and restrained to be comparable in magnitudes utilizing SHELX SIMU instructions.

SCXRD throughout gasoline sorption

A sequence of SCXRD experiments have been undertaken utilizing a gasoline rig and a gasoline cell on a dual-source Rigaku Synergy FR-X rotating anode diffractometer (Supplementary Section 2) and at beamline I19 at Diamond Light Source⁵⁷, to research the adsorption of CO₂ gasoline molecules in single crystals of 1–5. After preliminary crystal construction determinations, every crystal was uncovered to 10 bar CO₂ stress. A sequence of knowledge collections was undertaken on crystals of 1–5 whereby the temperature was progressively decreased to 200 Ok (232 Ok for 1). In the crystal construction fashions, CO₂ molecules had been positioned from distinction electron density maps and refined as inflexible our bodies with unconstrained occupancies. Isotropic displacement parameters for atoms of the CO₂ molecules had been constrained to U_iso = 0.2 Ų.

Data collected for compound 1 below CO₂ atmospheres (1^CO2) resulted in a low completeness (~91%) because the strongest reflections collected had been handled as detector overloads and omitted from refinements. Data collected for compound 2^CO2 (200 Ok, 10 bar CO₂), 3_B^CO2 (200 Ok, 10 bar CO₂) and 4^CO2 (200 Ok, 10 bar CO₂) had decrease resolutions than different knowledge (d_min ≈ 1 Ǻ). Crystal knowledge are summarized in Supplementary Tables 1–9

PXRD throughout gasoline sorption

The structural modifications related to CO₂ gasoline sorption by compounds 1, 2, 4 and 5, and CH₄ gasoline sorption by compounds 1 and 5 had been monitored in situ by powder X-ray diffraction at beamline ID31^58,59 on the European Synchrotron Radiation Source (ESRF) utilizing a nine-channel multi-analyser crystal detector and at beamline I11 on the Diamond Light Source utilizing a wide-angle (90°) position-sensitive detector comprising 18 Mythen-2 modules^60,61. For knowledge collected utilizing the position-sensitive detector, a pair of scans associated by a 0.25° detector offset had been collected for every measurement to account for gaps between detector modules. All knowledge had been collected at room temperature for research of CO₂ adsorption, whereas for CH₄ adsorption knowledge had been collected at each room temperature and 180 Ok. Thirty-minute intervals between measurements had been used to permit for equilibration of the construction alongside the capillary at every stress. A pattern of colourless microcrystalline 1, 2, 4 and 5, synthesized as beforehand described, was evenly floor utilizing an agate pestle and mortar and loaded right into a 0.8-mm quartz capillary. The open finish of the capillary was hooked up by way of tightened Swagelok compression fittings to the stainless steel tubing of a gasoline dealing with rig that was additional linked by way of a sequence of faucets to a lecture bottle of CO₂ or CH₄ gasoline, a turbomolecular pump and an exhaust vent. The rig, together with the capillary, was first evacuated taking care to not disturb the powder within the capillary.

For 1, PXRD scans had been collected (−2.5 ≤ 2θ ≤ 12.5°) at beamline ID31 (λ = 0.39998 Å) at ESRF utilizing a scan velocity of 6° min⁻¹, throughout which the capillary was oscillated about its axis by an angle of roughly 150°. One sequence of scans was collected at room temperature (p_CO2: 0, 1.01, 4.21, 9.71, 19.71, 50.23, 19.51, 10.05, 4.31 and 1.13 bar; p_CH4: 0, 19.71, 42.00, 18.35, 8.81, 4.31 and 1.13 bar). In a second examine (CH₄ solely), PXRD patterns had been obtained at 180 Ok for CH₄ pressures of two, 5 and 25 bar. For CP 2, 10-s PXRD scans had been measured at beamline I11 (λ = 0.826741(1) Å) at Diamond Light Source, throughout which the capillary was oscillated about its axis by an angle of roughly 35°. All knowledge had been collected at room temperature (p_CO2: 0, 1.19, 4.35, 5.15, 6.78, 7.68, 8.75, 11.07, 12.37, 15.52, 17.58, 19.16, 22.18, 49.23, 22.28, 18.55, 16.62, 14.33, 12.55, 10.33, 7.92, 5.05 and 1.4 bar). For CP 4, 10-s PXRD scans had been measured at beamline I11(λ = 0.826179(1) Å) at Diamond Light Source, throughout which the capillary was oscillated about its axis by an angle of roughly 35°. All knowledge had been collected at room temperature (p_CO2: 0, 1.13, 10.25, 14.54, 19.99, 24.40, 30.01, 49.90, 28.60, 25.05, 20.10, 10.31 and 1.04 bar). For CP 5, 10-s PXRD scans had been measured at beamline I11(λ = 0.826179(1) Å) at Diamond Light Source, throughout which the capillary was oscillated about its axis by an angle of roughly 35°. All knowledge had been collected at room temperature (p_CO2: 0, 1.02, 9.89, 14.89, 20.17, 24.24, 28.99, 38.53, 48.37, 49.41, 20.71, 15.60, 9.72 and 1.04 bar). In a separate experiment, knowledge had been collected at room temperature (295 Ok) and 180 Ok, every in a sequence of CH₄ gasoline pressures, (295 Ok, air; 180 Ok, p_CH4: 4.99, 9.63, 14.24, 18.63, 14.19, 10.14, 5.23 and 1.05 bar). All powder patterns had been listed and unit cell values had been decided by Pawley refinement utilizing TOPAS^62,63,64.

Volumetric and gravimetric gasoline sorption

Volumetric adsorption measurements had been undertaken utilizing a Micromeritics ASAP2420 Accelerated Surface Area and Porosimetry System. The samples had been degassed below vacuum in a single day earlier than evaluation, carried out utilizing nitrogen adsorption at 77 Ok (99.99% nitrogen adsorbate). A complete of 49 factors had been taken on the adsorption department and 30 on the desorption department. Gravimetric adsorption measurements had been recorded utilizing an Intelligent Gravimetric Analyser mannequin 003 equipped by Hiden Isochema Ltd. The stability and stress management system of the instrument are absolutely thermostatted to 0.1 Ok and the microbalance has a weighing decision of 0.2 μg. Samples (1–5) had been outgassed till they reached a relentless mass, at a stress of <10⁻⁶ mbar at 273 Ok. During measurements, the stress of the gasoline was step by step elevated over ~15 s avoiding disruption to the microbalance. Pressure management used a 0–2 MPa stress transducer, with an accuracy of 0.02 MPa. The stress was maintained on the set level by energetic pc management. The mass uptake was measured as a operate of time and the method to equilibrium monitored in actual time with a pc algorithm. After equilibrium was established, the stress of gasoline within the system was elevated to the following set stress worth and the next uptake was measured till equilibrium was re-established. Pressure steps within the vary of 0–20 bar had been used to acquire CO₂ isotherms for all compounds at 273 Ok. Additional CO₂ isotherms had been measured for samples 1–3 and 5 at 253 Ok and for 4 at 258 Ok and 263 Ok. Pressure steps within the vary of 0–10 bar had been used to acquire CH₄ isotherms for compounds 1 and 2 at 273 Ok. Further combined gasoline isotherms (90/10 or 80/20 CO₂/CH₄) had been measured (0–10 bar) for compounds 1 and 2 at 273 Ok to research selectivity between the 2 gases. During gasoline adsorption, the pattern temperature was maintained utilizing a thermostirrer and was continuously monitored all through the period of the experiment. All measurements had been made utilizing task-specific software program, equipped by Hiden Isochema Ltd.