Marie Savonnet

Solvent free base catalysis and transesterification over basic functionalised Metal-Organic Frameworks

Metal-Organic Frameworks (post-)functionalised with nitrogen containing moieties undergo solvent free aza-Michael condensation and transesterification, surpassing molecular and functionalised MCM-type analogues.

Tailoring Metal–Organic Frameworks for CO2 Capture: The Amino Effect

Carbon dioxide capture from processes is one of the strategies adopted to decrease anthropogenic greenhouse gas emissions. To lower the cost associated with the regeneration of amine-based scrubber systems, one of the envisaged strategies is the grafting of amines onto high-surface-area supports and, in particular, onto metal-organic frameworks (MOFs). In this study, the interaction between CO(2) and aliphatic and aromatic amines has been characterized by quantum mechanical methods (MP2), focusing attention both on species already reported in MOFs and on new amine-based linkers, to inspire the rational synthesis of new high-capacity MOFs. The calculations highlight binding-site requisites and indicate that CO(2) vibrations are independent of the adsorption energy and monitoring them in probe-molecule experiments is not a suitable marker of efficient adsorption.

Combinatorial synthesis of metal–organic frameworks libraries by click-chemistry

A key to address advanced MOF materials suitable for more sophisticated applications is to add functionalities of greater complexity in a controlled manner. We report a generic and original post-synthetic modification method starting from amino derived MOFs. The first step consists in converting the amino group into azide (N3). Without isolation nor purification, the desired functionalized material is obtained by grafting the corresponding alkyne using “Click Chemistry”. This work reports for the first time the synthesis of a two-dimensional combinatorial library of 24 functionalized MOFs. We also show that the grafting yield can be controlled from 10 to 100%. Finally, we compare the effect of the grafting yield on the porous volume of (1D) and (3D)MOF porous structures.

Cu-mediated solid-state reaction in a post-functionalized metal–organic framework

We serendipitously found that a functionalized MOF containing grafted copper species can react with itself without solvent in order to modify the chemical functions present on its walls. The use of EPR techniques allows new insight into the copper-mediated azide reduction.

Soft synthesis of isocyanate-functionalised metal–organic frameworks

We have developed an original synthetic pathway for the conversion of a MIL-68(In)-NH(2) metal-organic framework into its corresponding isocyanate (-NCO) derivative. This two-step soft post-modification technique leads to highly porous isostructural materials.