Kinetic Assembly of a Thermally Stable Porous Coordination Network Based on Labile CuI Units and the Visualization of I₂ Sorption

Abstract

A net gain: A kinetically assembled, but thermally stable network is obtained using the labile metal species [Cu4 I4 (PPh3 )4 ]. The network uniquely adsorbs I2 by chemisorption through I3 (-) formation. The chemisorbed I2 readily desorbs above 380 K owing to the dynamic motion of the framework. A thermodynamically assembled network physisorbs I2 , which is an exact fit for the channel.

Effect of the Redox Properties of the Zinc and Nickel Metal–Organic Frameworks on Peculiarities of Their Interaction with Iodine and the Electronic Conductivity of the Composites Formed

“…On the other hand, this reaction has pseudo-second-order kinetics in the final segment with rate constant k 2 = 2.5·10 -4 g·mg -1 ·min -1 . Taking account of the quasi-stationary conditions of this experiment, we can propose that the first-order kinetics seen for the initial segment of the curve for 2 is the result of iodine diffusion in solution as the rate-limiting step, while the rate-limiting step in the second-order reaction is the chemisorption of iodine [24]. We should note that the amount of iodine adsorbed by the MOF studied upon reaching the equilibrium state differs by a factor of 4 depending on the nature of the metal ion: 15 mg/g (0.03 mole I 2 per mole adsorbent) and 59 mg/g (0.11 mole I 2 per mole adsorbent) for 1 and 2, respectively.…”

Reversible flexible structural changes in multidimensional MOFs by guest molecules (I2, NH3) and thermal stimulation

“…Preliminary experiments were conducted in which Material 2 was activated at 150 1C for 2 h or soaked in MeOH for several days, it is then transformed into Material 1 by the release of I 2 ; Material 3 was activated at 150 1C for 2 h, it is then transformed into Material 1 by releasing NH 3 and H 2 O. There are several cases like this in which structures change by the removal of guest or solvent molecules; however, there are few reports of these structures reverting back to their original form [27][28][29]. Here, we implemented the experiment of adsorbing I 2 or NH 3 to verify the reversible transformation of the three materials.…”

Flexible Zirconium MOFs as Bromine‐Nanocontainers for Bromination Reactions under Ambient Conditions

“…Recently,al arge number of rigid porous materials including MOFs were explored as iodine absorbents with relatively high adsorption capacities. [8] Commendably,aredox-active MOF, Co 2 Cl 2 BTDD,w as employed for the reversible capture and release of gaseous Cl 2 and Br 2 . [9] FMOFs that undergo structure evolution upon guest uptake are particularly promising for adsorption and storage applications because this can lead to increased adsorption enthalpy,e nhanced selectivity and high usable storage capacities.F or example,t he Long group developed as eries of FMOFs for methane storage with intrinsic thermal management.…”

“…[8] Commendably,aredox-active MOF, Co 2 Cl 2 BTDD,w as employed for the reversible capture and release of gaseous Cl 2 and Br 2 . Recently,al arge number of rigid porous materials including MOFs were explored as iodine absorbents with relatively high adsorption capacities.…”