Control over Catenation in Pillared Paddlewheel Metal–Organic Framework Materials via Solvent-Assisted Linker Exchange

Abstract

Control over catenation in a pillared paddlewheel metal−organic framework was achieved via solventassisted linker exchange. The linker exchange was demonstrated on the noncatenated structure of DO-MOF, by using 4,4′-bipyridine (L4) and 4,4′-azobis(pyridine) (L5) as linkers, leading to noncatenated materials SALEM-3 and SALEM-4. The de novo synthesized analogues of SALEM-3 and SALEM-4 can only be obtained as 2-fold interpenetrated frameworks. The reaction progress of the linker exchange was monitored by NMR spectroscopy, and structure and framework catenation were characterized by powder X-ray diffraction and thermogravimetric methods.

Interpenetration in coordination polymers: structural diversities toward porous functional materials

“…For example, Hupp et al reported control of interpenetration through designing a dibromo substituted tetracarboxylic acid where the two bulky bromine atoms occupy the free spaces in 2D layer; hence further accommodation of extra networks is not possible [91]. Hupp et al also reported an excellent solvent assisted linker exchange (SALE) procedure for controlling interpenetration [92]. They initially synthesized a non-interpenetrated DO-MOF with combination of Zn(II), L1 and diol containing L3 (L1 = 4,4 0 ,4 00 ,4 000 -benzene-1,2,4,5-tetrayl-tetrabenzoate; L3 = 1,2-di(pyridin-4-yl)ethane-1,2-diol).…”

Direct photo-hydroxylation of the Zr-based framework UiO-66

“…azides, are not stable under the conditions required for framework assembly. 15 While several important discoveries have been reported using these methods, the transformation of unfunctionalised frameworks remains relatively underdeveloped; 16 in particular, the direct functionalisation of aromatic rings within MOFs 17 appears to be a more challenging prospect given incompatibilities between the often harsh chemistry involved and framework stability and the potential to yield unwanted side products. 12 More recently, MOFs have also been subjected to post-synthetic linker exchange (PSLE) processes where ligands bound to the metal clusters are readily exchanged by linkers bearing similar metal-binding functionality.…”

Nitro‐Functionalized Bis(pyrazolate) Metal–Organic Frameworks as Carbon Dioxide Capture Materials under Ambient Conditions

“…GCMC simulations were run on two models, namely, the orthorhombic and tetragonal crystal structures obtained from PXRD; the unit cells were then subject to geometry optimization on the basis of molecular mechanics, modifying the atomic coordinates but not the unit‐cell parameters. These calculations were performed with the Forcite module of Materials Studio by using an algorithm that was a cascade of the steepest descent, adjusted basis set Newton–Raphson, and quasi‐Newton methods . The bonding and the short‐range (van der Waals) interactions between atoms were modeled by using UFF.…”

“…These calculations were performed with the Forcite module of Materials Studio by using an algorithm that was ac ascade of the steepest descent, adjusted basis set Newton-Raphson, and quasi-Newton methods. [69][70][71] The bonding and the short-range (van der Waals) interactions between atoms were modeled by using UFF.Ac ut-off distance of 18.5 was used for the van der Waals interactions during geometry optimization.…”