Stabilizing Porosity in Organic Cages through Coordination Chemistry

Deegan, Meaghan M.; Bhattacharjee, Rameswar; Caratzoulas, Stavros; Bloch, Eric D.

doi:10.1021/acs.inorgchem.0c03590

Cited by 11 publications

(9 citation statements)

References 41 publications

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“…Our recently reported metalated porous organic cages represent an incredibly tunable reagent for this approach. 52 Reduction of the imine-based porous organic cage, CC1, affords an aminebased cage that has ethylenediamine-type binding pockets at its vertices. These can be postsynthetically metalated with a variety of transition metal cations.…”

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“…Porous salts have the advantage in that the identity of metals in the product phases and the ratio between them are governed by the starting materials used in their synthesis. Our recently reported metalated porous organic cages represent an incredibly tunable reagent for this approach . Reduction of the imine-based porous organic cage, CC1, affords an amine-based cage that has ethylenediamine-type binding pockets at its vertices.…”

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Elaboration of Porous Salts

et al. 2021

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A large library of novel porous salts based on charged coordination cages was synthesized via straightforward salt metathesis reactions. For these, solutions of salts of oppositely charged coordination cages are mixed to precipitate MOF-like permanently porous products where metal identity, pore size, ligand functional groups, and surface area are highly tunable. For most of these materials, the constituent cages combine in the ratios expected based on their charge. Additional studies focused on the rate of salt metathesis or reaction stoichiometry as variables to tune particle size or product composition, respectively. It is expected that the design principles outlined here will be widely applicable for the synthesis of new porous salts based on a variety of charged porous molecular precursors.

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Elaboration of Porous Salts

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“…The macrostructures shown are obviously not rigid and will collapse under local optimization or during molecular dynamics simulation. The stability of porous cages, or rather a lack thereof, is a well-known problem in porous organic cages (POC) and metal–organic frameworks (MOF), but successful countermeasures are being researched. − Another possible stabilization route employs host–guest complexes. Indeed, by enclosing a guest structure, we can stabilize the macromolecule and perform a local geometry optimization without qualitative structure changes.…”

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Graph-based Automated Macro-Molecule Assembly

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Hartke

2022

J. Chem. Inf. Model.

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We present a general molecular framework assembly algorithm that takes a largely arbitrary molecular fragment database and a user-supplied target template graph as input. Automatic assembly of molecular fragments from the database, following a prescribed, user-supplied set of connection rules, then turns the template graph into an actual, chemically reasonable molecular framework. Assembly capabilities of our algorithm are tested by producing several abstract, closed-loop shapes. To indicate a few of many possible application areas we demonstrate a host–guest complex and a road toward catalysis. Postassembly substituent exchange can be used to produce electric fields of desired values at desired points inside the framework or at its surface as a stepping stone toward rationally designed, artificial heterogeneous catalysts.

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“…As a result, we observed a high Brunauer−Emmett−Teller (BET) area of 1260 m 2 /g for NU-1107 (Figure 3c) while retaining comparable crystallinity to that of the as-synthesized sample prior to activation (Figure 3b). For the metalated samples, we envisioned that metalation of the cyclen linker would significantly enhance the framework rigidity, 53 so we attempted a conventional thermal activation for these samples. However, NU-1107-Cu showed moderate porosity (BET area: 730 m 2 / g) or low porosity (BET area: 300 m 2 /g) when exchanged with acetone followed by activation at room temperature or 60 °C, respectively (Figure S8).…”

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Programmed Polarizability Engineering in a Cyclen-Based Cubic Zr(IV) Metal–Organic Framework to Boost Xe/Kr Separation

et al. 2023

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Efficient separation of xenon (Xe) and krypton (Kr) mixtures through vacuum swing adsorption (VSA) is considered the most attractive route to reduce energy consumption, but discriminating between these two gases is difficult due to their similar properties. In this work, we report a cubic zirconium-based MOF (Zr-MOF) platform, denoted as NU-1107, capable of achieving selective separation of Xe/Kr by post-synthetically engineering framework polarizability in a programmable manner. Specifically, the tetratopic linkers in NU-1107 feature tetradentate cyclen cores that are capable of chelating a variety of transition-metal ions, affording a sequence of metal-docked cationic isostructural Zr-MOFs. NU-1107-Ag(I), which features the strongest framework polarizability among this series, achieves the best performance for a 20:80 v/v Xe/Kr mixture at 298 K and 1.0 bar with an ideal adsorbed solution theory (IAST) predicted selectivity of 13.4, placing it among the highest performing MOF materials reported to date. Notably, the Xe/Kr separation performance for NU-1107-Ag(I) is significantly better than that of the isoreticular, porphyrin-based MOF-525-Ag(II), highlighting how the cyclen core can generate relatively stronger framework polarizability through the formation of low-valent Ag(I) species and polarizable counteranions. Density functional theory (DFT) calculations corroborate these experimental results and suggest strong interactions between Xe and exposed Ag(I) sites in NU-1107-Ag(I). Finally, we validated this framework polarizability regulation approach by demonstrating the effectiveness of NU-1107-Ag(I) toward C3H6/C3H8 separation, indicating that this generalizable strategy can facilitate the bespoke synthesis of polarized porous materials for targeted separations.

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Stabilizing Porosity in Organic Cages through Coordination Chemistry

Cited by 11 publications

References 41 publications

Elaboration of Porous Salts

Elaboration of Porous Salts

Graph-based Automated Macro-Molecule Assembly

Programmed Polarizability Engineering in a Cyclen-Based Cubic Zr(IV) Metal–Organic Framework to Boost Xe/Kr Separation

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