Dual metal organic framework post-synthetic modification; two birds with one stone.

Simultaneous dual post-synthetic modification was realised in multivariate isoreticular zinc 4,4'-biphenyldicarboxylate frameworks co-loaded with thermo-reactive allyloxy and propargyloxy groups. Radiative heating initiates dual cascade reactions, simultaneously changing both groups under the same conditions with preservation of framework topology and porosity. This work provides a new strategy to target multiple groups in shorter sequences for more efficient metal-organic framework post-synthetic modification.

Trisequential Postsynthetic Modification of a Tagged IRMOF-9 Framework.

Tailoring the pore environments of metal-organic frameworks (MOFs) is key to improving their performance and expanding their applicability. Postsynthetic methods, wherein an already synthesized MOF undergoes further chemical reactions, present many advantages for such tailoring and lead to much interesting new chemistry. However, this method has seldom been pushed farther than two reaction steps on the organic component.

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid.

The synthesis, structural and thermal characterisation of a number of coordination complexes featuring the N,O-heteroditopic ligand 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate, HL are reported. The reaction of H2L with cobalt(II) and nickel(II) nitrates at room temperature in basic DMF/H2O solution gave discrete mononuclear coordination complexes with the general formula {[M(HL)2(H2O)4]·2DMF} (M = Co (1), Ni (2)), whereas the reaction with zinc(II) nitrate gave [Zn(HL)2]∞, 3, a coordination polymer with distorted diamondoid topology and fourfold interpenetration. Coordination about the tetrahedral Zn(II) nodes in 3 are furnished by two pyrazolyl nitrogen atoms and two carboxylate oxygen atoms to give a mixed N2O2 donor set.

A reagentless thermal post-synthetic rearrangement of an allyloxy-tagged metal-organic framework.

Direct heating of a metal-organic framework provides a simple, controllable way of effecting a covalent post-synthetic modification. Herein we report that an allyloxy-tagged zinc metal-organic framework undergoes a thermally-promoted aromatic Claisen rearrangement through which the framework connectivity and porosity are maintained.