Guest-selective shape-memory effect in a switchable metal-organic framework DUT-8(Zn).

Crystal size engineering allows tailoring of flexible metal-organic frameworks (MOFs) to achieve new properties. The gating type flexibility of the DUT-8(Zn) ([Zn2(2,6-ndc)2(dabco)]n, 2,6-ndc = 2,6-naphthalene dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane) compound is known to be extremely particle size sensitive. Here, the physisorption of ethanol vapor gives rise to so-called shape-memory effect, leading to rigidification and flexibility suppression. According to powder X-ray diffraction and nitrogen physisorption experiments, the open pore phase is retained selectively after desorption of alcohols, which could be attributed to the nano-structuring and surface deformation of the crystals as a result of exposure to alcohols.

Particle size-dependent flexibility in DUT-8(Cu) pillared layer metal-organic framework.

The nature of metal in the isomorphous flexible metal-organic frameworks is often reported to influence flexibility and responsivity. A prominent example of such behaviour is the DUT-8(M) family ([M2(2,6-ndc)2(dabco)]n, 2,6-ndc = 2,6-naphthalene dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane), where the isostructural compounds with Ni, Zn, Co, and Cu in the paddle wheel cluster are known. The macro-sized crystals of Ni, Co, and Zn based compounds transform to the closed pore (cp) phase under desolvation and show typical gate opening behaviour upon adsorption. The choice of metal, in this case, allows the adjustment of switching kinetics, selectivity in adsorption, and gate-opening pressures. The submicron-sized crystals of of Ni, Co, and Zn based compounds remain in the open pore (op) phase after desolvation. In this contribution, we demonstrate that the presence of Cu in the paddle wheel leads to fundamentally different flexible behaviour. The DUT-8(Cu) desolvation does not lead to the formation of the cp phase, independent of the particle size regime. However, according to in situ powder diffraction analysis, the desolvated, macro-sized crystals of DUT-8(Cu)_op show breathing upon adsorption of CO2 at 195 K. The submicron-sized particles show rigid, nonresponsive behaviour.

The Dilemma of Reproducibility of Gating Isotherms for Flexible MOFs.

Porous materials receive a high level of scientific and technological interest due to their applications in various fields such as adsorption, separation and storage, catalysis, ion exchange, nanotechnology, etc. Gas adsorption is a well-established tool for the characterization of the texture of porous solids. Physisorption isotherms are generally expected to be well reproducible for rigid adsorbents, but this is not always the case for nonrigid (flexible) materials. The presence of a metastability region and sensitivity of the activation barriers to the material's texture often influence the isotherms' run. Here, we address the complexity that arises in terms of reproducibility and sample handling for flexible metal-organic frameworks, with the example of DUT-8(Ni). It belongs to the group of "gate opening" metal-organic frameworks and is a typical representative of the pillared layer compounds. We propose characteristic parameters for the analysis and comparison of adsorption isotherms, showing the "gate opening" step, associated with the adsorption-induced solid-state phase transition. A set of 50 nitrogen physisorption isotherms measured at 77 K were analyzed and correlated with the synthetic and outgassing conditions. The study highlights the importance of accurate descriptions and record-keeping of experimental details and their role in the replication of scientific results.

Isotope-selective pore opening in a flexible metal-organic framework.

Flexible metal-organic frameworks that show reversible guest-induced phase transitions between closed and open pore phases have enormous potential for highly selective, energy-efficient gas separations. Here, we present the gate-opening process of DUT-8(Ni) that selectively responds to D2, whereas no response is observed for H2 and HD. In situ neutron diffraction directly reveals this pressure-dependent phase transition. Low-temperature thermal desorption spectroscopy measurements indicate an outstanding D2-over-H2 selectivity of 11.6 at 23.3 K, with high D2 uptake. First-principles calculations coupled with statistical thermodynamics predict the isotope-selective gate opening, rationalized by pronounced nuclear quantum effects. Simulations suggest DUT-8(Ni) to remain closed in the presence of HT, while it also opens for DT and T2, demonstrating gate opening as a highly effective approach for isotopolog separation.

Linker Expansion and Its Impact on Switchability in Pillared-Layer MOFs.

Linker elongation is an important method to systematically adjust porosity and pore size in isoreticular MOFs. In flexible structures, this approach opens the possibility for the systematic analysis of the building blocks and their contribution to the overall flexible behavior enabling tuning of the framework responsivity toward molecular stimuli. In this work, we report two new compounds isoreticular to the highly flexible pillared layer structure DUT-8(Ni) ([Ni2(2,6-ndc)2(dabco)]n, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicylo[2.2.2]octane). Aromatic linker 2,6-ndc was substituted by longer carboxylic linkers, namely, 4,4'-biphenyldicarboxylate (4,4'-bpdc) and 4,4'-stilbenedicarboxylate (4,4'-sdc), while the dabco pillar was retained. The structural response of the new compounds toward the desolvation and adsorption of various fluids was studied using advanced in situ PXRD techniques, demonstrating distinct differences in the flexible behavior of three compounds and disclosing the impact of linker structure on the framework response. Theoretical calculations provide mechanistic insights and an energetic rationale for the pronounced differences in switchability observed. The energetics of linker bending and linker-linker dispersion interactions govern the phase transitions in investigated MOFs.

Single particle Raman spectroscopy analysis of the metal-organic framework DUT-8(Ni) switching transition under hydrostatic pressure.

Experimental in situ observations of phase coexistence in switchable metal-organic frameworks are reported to provide a fundamental understanding of dynamic adsorbents that can change their pore structure in response to external stimuli. A prototypical flexible pillared layer framework DUT-8(Ni) (DUT = Dresden University of Technology) was studied under hydrostatic pressure by in situ Raman spectroscopy on single crystals. The closing transition of the open pore phase (op) containing DMF in the pores in silicon oil as a pressure transmitting fluid, as well as the closed pore phase (cp) to op transition under pressure in methanol, were studied. Phase coexistences during both transitions were observed.

Raman spectroscopy studies of the terahertz vibrational modes of a DUT-8 (Ni) metal-organic framework.

Low-frequency lattice vibrational modes have been discussed to play a crucial role in the phase transformation process of flexible metal-organic frameworks (MOFs). Therefore, Raman spectroscopy was applied to study the lattice dynamics of a pillared layer DUT-8(Ni) framework (DUT - Dresden University of Technology), existing in rigid and flexible forms. Both the open and the close pore phases could be unambiguously identified by breathing mode bands at 23 cm-1 and 60 cm-1 in the corresponding Raman spectra, showing the efficiency of the technique for monitoring the flexibility of MOF materials as well as the differences in the lattice vibrations of the two phases. Born-Oppenheimer Molecular Dynamics simulations showed that observed low-frequency bands indeed correspond to the oscillation of the breathing mode along the diagonals of the pore channels. Moreover, the directional character of low-frequency vibrations in the flexible version of DUT-8(Ni) could be visualized by the orientation dependent Raman spectroscopy experiment.