Drinking and Breathing: Solvent Coordination‐driven Plasticity of IRMOF‐9

Abstract

The coordination chemistry of Metal-Organic Frameworks is one key aspect when their applications and performances enhancement are pursued. This is usually investigated while cation exchanges or functionalisation reactions on open metal sites are involved. In this work we present a rare case of solvent coordination-induced breathing behaviour of a renowned Zn-based MOF, namely IRMOF-9, whose structural flexibility allows its framework topology to be retained upon dramatic coordination changes on their inorganic nodes. These are observed to accept from one to three additional coordination bonds from solvent molecules, depending on the coordination power of these latter and on temperature conditions. Structural studies by Single Crystal X-Ray Diffraction afforded precious insights on the occurring of such coordinative changes, suggesting that solvent molecules which dynamically bind the metal atoms are capable to play a decisive role in the final geometry of the framework.

Reversible mechanochromic studies on AIE-inspired smart materials and their applications in HCHO sensing

“…[23][24][25] The stimulus-responsive phenomenon is usually observed in metal-organic frameworks (MOFs), as they could display dynamic changes in the interactions between the network components or changes in the coordination environment of transition metals. [26][27][28][29] In this respect, aggregationinduced emission (AIE) systems based on tetraphenylethylene (TPE) and its derivatives readily undergo fluorescence transformation under a stimulus due to the flexible rotation of their phenyl rings and twisting of the CvC bond, thus attracting much more attention and leading to rapid developments. [30][31][32][33] However, the subsequent fluorescent restoration to the original state is usually achieved by some accidental solvent fumigation treatment.…”

Using Machine Learning and Data Mining to Leverage Community Knowledge for the Engineering of Stable Metal–Organic Frameworks

“…Indeed, this changes the predicted solvent-removal stability from unstable to stable (0.11 vs 0.89) while preserving the prediction of good thermal stability (433 °C vs 430 °C, Figure ). A subsequent search of the CSD confirms these modifications are synthetically accessible because they have already been carried out to make a stable MOF (refcode: PIWLIT) not present in the CoRE MOF database and thus not in our data sets. However, a lack of experimental TGA data in that manuscript prevents explicit validation of our prediction that the thermal stability should be unchanged.…”

Pressure-Induced Postsynthetic Cluster Anion Substitution in a MIL-53 Topology Scandium Metal-Organic Framework

“…Kinetically labile bonds between metals and ligands can allow access to coordinatively unsaturated metal sites [2][3][4] that endow MOFs with catalytic properties, [5][6][7] enhance their interactions with sorbates such as H2, [8][9][10][11] and offer potential sensing mechanisms. [12][13][14] Dynamic SBU solvent substitution can facilitate structural flexibility 15,16 and metal-ion exchange, 17,18 while also offering routes to pore functionalisation through linker exchange, [18][19][20][21][22] linker incorporation/grafting, [23][24][25][26] and defect substitution. [27][28][29][30][31][32][33] Coordinative exchange reactions may also be responsible for MOF degradation, for example through hydrolysis.…”