Rapid Cs+ Capture via Multiple Supramolecular Interactions in Anionic Metal-Organic Framework Isomers.

Metal-organic frameworks (MOFs) provide an ideal platform for ion exchange due to their high porosity and structural designability; however, developing MOFs that have the essential characteristics for ion exchange remains a challenge. These crucial features include fast kinetics, selectivity, and stability. We present two anionic isomers, DGIST-2 (2D) and DGIST-3 (3D), comprising distinctly arranged 5-(1,8-naphthalimido)isophthalate ligands and In3+ cations. Interestingly, in protic solvents, DGIST-2 transforms into a hydrolytically stable crystalline phase, DGIST-2'. DGIST-2' and DGIST-3 exhibit rapid Cs+ adsorption kinetics, as well as high Cs+ affinity in the presence of competing cations. The mechanism for rapid and selective sorption is explored based on the results of single-crystal X-ray diffraction analysis of Cs+-incorporated DGIST-3. In Cs+-containing solutions, the loosely incorporated dimethylammonium countercation of the anionic framework is replaced by Cs+, which is held in the hydrophobic cavity by supramolecular ion-ion and cation-π interactions.

Comprehensive Qualitative and Quantitative Colorimetric Sensing of Volatile Organic Compounds Using Monolayered Metal-Organic Framework Films.

Cross-responsive chemical sensors are in high demand owing to their ability to distinguish a broad range of analytes. In this study, a vapochromic sensor array based on metal-organic frameworks (MOFs), which exhibits distinct patterns when exposed to volatile organic compounds (VOCs) and humidity, is developed. Conventional sensor arrays consist of various receptors that produce different responses. The vapochromic MOF-based sensor comprises dicopper paddlewheel clusters and dimethylamine azobenzene as binary colorimetric sensing moieties. Upon exposure to VOCs, the constructed sensor encompasses a broad spectrum of colors, ranging from green to red. Furthermore, the color of the MOF is influenced by the solvent used during the pretreatment. Consequently, monolayered MOF thin films can be adapted to multicomponent array systems by immersing the MOF in different solvents. This system provides both qualitative and quantitative sensing, generating unique color patterns corresponding to specific VOC types. Notably, the sensor successfully discriminates each of 14 common VOCs and water and accurately categorizes unknown samples. Moreover, the system undergoes reversible color changes in response to humidity, obviating the need for high-temperature regeneration steps. This novel approach offers insights into the versatile applications of MOFs by creating a colorimetric sensor array capable of detecting various analytes.

Solvent-induced structural transformation in a one-dimensional coordination polymer.

We have rationally designed a one-dimensional coordination polymer (1D CP), termed 1D-DGIST-18, that exhibits intrinsic structural flexibility. This 1D CP enables its expansion into a three-dimensional network through supramolecular interactions involving coordinated solvents and/or ligands. The strategic selection of solvents for solvent exchange, prior to drying, significantly influences the structures of 1D-DGIST-18 by removing certain coordinating solvents and modulating π-π stacking. Consequently, a hierarchical porosity emerges, ranging from micro- to meso- to macroporous structures, which is attributed to its inherent structural dynamics. Additionally, the formation of excimers endows 1D-DGIST-18, when immersed in acetone, with 'turn-on' fluorescence, as evidenced by fluorescence decay profiles. These structural transitions within 1D-DGIST-18 are further elucidated using single-crystal X-ray diffractometry. The insights from this study provide a foundation for the design of materials with structural dynamics and tunable properties.

Carboxylate-functionalized organic nanocrystals for high-capacity uranium sorbents.

Carboxylate-functionalized organic nanocrystals (ONCs) derived from perylene diimide or naphthalene diimide were synthesized and carefully characterized as novel high-capacity uranium (U(VI)) sorbents. Adsorption studies using uranyl ions demonstrated that the carboxyl and hydroxyl groups on the surface of the ONCs play pivotal roles in U(VI) adsorption. ONCs formed from the condensation of perylene dianhydride and aminoisophthalic acid exhibit very high U(VI) adsorption capacities of 1393 mg g-1 comparable to the highest capacity ever reported. The adsorption kinetics of the ONCs were found to obey the second-order model, indicating that chemisorption is the rate-determining step for U(VI) adsorption by these materials. Furthermore, the perylene-based ONC containing imidazole exhibited no pH dependency upon the U(VI) adsorption and the naphthalene-based ONC was able to remove up to 97.5% U(VI) from simulated nuclear industrial effluent containing many competing elements. These findings will facilitate the development of high-performance organic U(VI) sorbents with high densities of adsorption sites.