September 2024
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4 Reads
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September 2024
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4 Reads
March 2024
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32 Reads
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2 Citations
Langmuir
February 2024
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33 Reads
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5 Citations
Crystal Growth & Design
January 2024
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17 Reads
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2 Citations
Crystal Growth & Design
January 2024
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16 Reads
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2 Citations
Chemical Communications
Systematic replacement of selenium for tellurium in a chalcogen-bonding tecton results in divergent assembly behavior from competitive solvents.
September 2023
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36 Reads
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21 Citations
Journal of the American Chemical Society
June 2023
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13 Reads
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6 Citations
Crystal Growth & Design
March 2023
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41 Reads
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17 Citations
Journal of the American Chemical Society
Step-shaped adsorption-desorption of gaseous payloads by flexible metal-organic frameworks can facilitate the delivery of large usable capacities with significantly reduced energetic penalties. This is desirable for the storage, transport, and delivery of H2, as prototypical adsorbents require large swings in pressure and temperature to achieve usable capacities approaching their total capacities. However, the weak physisorption of H2 typically necessitates undesirably high pressures to induce the framework phase change. As de novo design of flexible frameworks is exceedingly challenging, the ability to intuitively adapt known frameworks is required. We demonstrate that the multivariate linker approach is a powerful tool for tuning the phase change behavior of flexible frameworks. In this work, 2-methyl-5,6-difluorobenzimidazolate was solvothermally incorporated into the known framework CdIF-13 (sod-Cd(benzimidazolate)2), resulting in the multivariate framework sod-Cd(benzimidazolate)1.87(2-methyl-5,6-difluorobenzimidazolate)0.13 (ratio = 14:1), which exhibited a considerably reduced stepped adsorption threshold pressure while maintaining the desirable adsorption-desorption profile and capacity of CdIF-13. At 77 K, the multivariate framework exhibits stepped H2 adsorption with saturation below 50 bar and minimal desorption hysteresis at 5 bar. At 87 K, saturation of step-shaped adsorption occurs by 90 bar, with hysteresis closing at 30 bar. These adsorption-desorption profiles enable usable capacities in a mild pressure swing process above 1 mass %, representing 85-92% of the total capacities. This work demonstrates that the desirable performance of flexible frameworks can be readily adapted through the multivariate approach to enable efficient storage and delivery of weakly physisorbing species.
February 2023
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15 Reads
Supramolecular Chemistry
September 2022
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13 Reads
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9 Citations
Chemical Communications
Through systematic linker substitution in a flexible zeolitic imidazolate framework (ZIF) with step-shaped adsorption-desorption, structural intermediates between the known open and closed phases were isolated. Reflecting this, modulative sorption behaviour with an inverting adsorption pressure trend-in which the step pressure decreases and then increases again with increasing mixed linker concentration-is observed, highlighting how linker substitution modifies the energetic landscape of framework flexibility.
... [10] Sulfated zirconium oxide (SZO) contains sulfates, pyrosulfates, and Brønsted acid sites. [11] Sulfation would also presumably increase electrophilicity at Zr that is expected to increase rates of heterolytic CÀ H bond activation reactions. [12] However, there is limited evidence that SZO can activate CÀ H bonds in alkanes by a heterolytic mechanism in Figure 1c, and most proposals assume Brønsted sites on SZO protonate CÀ H bonds to form carbocations. ...
March 2024
Langmuir
... [1][2][3] A significant volume of work has attempted to prepare permanently porous 3D framework materials using halogen bonds (XOFs). However, as recently pointed out by McGuirk, [4] no permanently porous halogen bonded material has been reported yet, and halogen bonded materials showing any kind of porosity are very rare. [5][6][7][8][9][10] This stands in contrast to materials prepared using analogous hydrogen bonds, with numerous permanently porous hydrogenbonded organic frameworks reported. ...
February 2024
Crystal Growth & Design
... [42][43][44] Owing to the rational design and precise control in pore engineering (including pore size, pore environment, and pore surface functionalization), which is a crucial factor in developing materials for gas adsorption separation, MOFs have been widely explored as adsorbents to address the challenging task of alkane/alkene separation. [45][46][47][48][49][50] In general, MOF adsorbents for alkane/alkene separation can be divided into two categories: alkene-selective or alkaneselective adsorbents. To date, most MOFs have demonstrated the alkene-selective capacity, generally relying on either open metal sites (OMSs) that provide preferential adsorption sites for alkene molecules compared to their saturated alkane analogues or kinetically controlled differences in diffusion rates. ...
September 2023
Journal of the American Chemical Society
... This behaviour is in contrast to other XB networks in which the nature of the solvent strongly influences structure geometry and pore size. [47] The crystals of 1·NaCl could be isolated by filtration, washing and air-drying for 2 min in 48-73 % yield depending on crystallisation solvent. While apparently stable out of solvent for short periods, the crystals grown from the volatile solvents CH 2 Cl 2 , CHCl 3 and THF did demonstrate some visual quality degradation-such as cracking-within minutes upon drying (see SI). ...
June 2023
Crystal Growth & Design
... Recently, McGuirk and co-workers [54] reported a mixed linker approach successfully induced flexibility in [Cd(benzimidazolate) 2 ] n (CdIF-13) framework, which shows negligible uptake at 77 K in the pressure range up to 100 bar (Figure 12). The 13% of 2-methyl-5,6-difluorobenzimidazolate (2M56DFbim) instead of benzimidazolate (b induces gateopening for H 2 . ...
March 2023
Journal of the American Chemical Society
... Possibly, the FWHM of the materials corresponding to Series 2 is larger due to the lower extent of crystallinity. While the FWHM parameter is frequently utilized to determine crystallite size, in the simplest way using Sherrer equation, such an analysis requires excluding other factors of peak broadening, such as instrumental broadening, inhomogeneous strain, crystal lattice imperfections, different degree of crystallinity etc.. [35] Notably, the results of SEM analysis show same trend of decrease of particle size with decreasing HCl/Zr ratio in Series 2 (Figures 1, S2 and S3, Table 1). ...
March 2022
Inorganic Chemistry
... This contrasts with the majority of experimental and theoretical studies of chalcogen bonding interactions that have measured their effects on thermodynamic equilibria [2,11,12,[20][21][22][23][24] using hostguest complexes or assemblies. [5,25,26] The magnitude and stability trends of ChBs in transition states are influenced by the crowded and compact structure of transition states, which often have distorted bond lengths and hypervalent atoms. [27] Isolating and measuring the effects of non-covalent interactions on kinetic processes is challenging. ...
November 2021
Journal of the American Chemical Society
... 7 As a result, a major focus has been on the development of building blocks which can undergo reversible transformations in response to an applied external stimulus (e.g., light, heat, pH, pressure, or current) and their methods of incorporation into various platforms. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] For example, integration of stimuli-responsive moieties in relatively large systems (e.g., polymers, supramolecular complexes, or periodic solids) has resulted in the development of tailorable supercapacitors, 25 artificial muscles, 26 and multilevel anticounterfeiting and information encryption methods. 27 While the majority of artificial systems rely on only one type of stimulus, many natural systems are much more complex and rely on networks of independently controlled processes based on inputs from multiple stimuli. ...
November 2021
... Due to their appealing properties such as structural and functional diversity, porous nature, size tunability, and enormous surface area. MOF is an attractive candidate for their potential applications in gas storage, [37][38][39][40][41][42] molecular separation, 40,[43][44][45][46][47][48][49][50] sensors, [51][52][53][54][55][56] and catalysis [57][58][59][60][61][62][63][64] among all other classical sorbent systems. The balance between the high gravimetric and volumetric adsorptive capacity of MOF makes them undeniably, a promising class of material for adsorptive gas storage application, apart from zeolites, COFs, and complex hydrides that are available for gas adsorption applications. ...
December 2019
Angewandte Chemie
... Sculley and Zhou [46] added zirconium content to the complex amine-supported porous silica systems for carbon capture (figure 4(c-ii)), which improved desorption kinetics effectively. Furthermore, as shown in figure 4(c-iii), amine solvents were combined with MOFs to realize the chemisorption of CO 2 [47]. ...
February 2020