An Adaptive Hydrogen-Bonded Organic Framework for the Exclusive Recognition of p-Xylene

Separation of xylene isomers is one of the most important but most challenging and energy-intensive separation processes in the petrochemical industry. Here, we report an adaptive hydrogen-bonded organic framework (HOF-29) constructed from a porphyrin based organic building block 4,4 ',4 '',4 '''-(porphyrin-5,10,15,20-tetrayl) tetrabenzonitrile (PTTBN), exhibiting the exclusive molecular recognition of p-xylene (pX) over its isomers of o-xylene (oX) and m-xylene (mX), as clearly demonstrated in the single crystal structure transformation and H-1 NMR studies. Single crystal structure studies show that single-crystal-to-single-crystal transformation from the as-synthesized HOF-29 to the pX exclusively included HOF-29 superset of pX is triggered by the encapsulation of pX molecules, accompanied by sliding of the 2D layers and local distortion of the ligand, which provides multiple C-H...pi interactions.