A Solid Transformation into Carboxyl Dimers Based on a Robust Hydrogen-Bonded Organic Framework for Propyne/Propylene Separation.

Self-assembly of N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine with the help of different solvents provides isostructural hydrogen-bonded organic frameworks (HOF-30). Single-crystal X-ray diffraction (SCXRD) analysis reveals HOF-30 possesses 3D ten-fold interpenetrated dia nets connected by two kinds of hydrogen bonds, namely solvent-bridged carboxyl dimers and carboxyl⋅⋅⋅carboxyl dimers. Degassing treatment for HOF-30 yields HOF-30a with 3D ten-fold interpenetrated dia nets but linked with sole carboxyl⋅⋅⋅carboxyl dimers. Reversible hydrogen-bond-to-hydrogen-bond transformation between solvent-bridged carboxyl dimers in HOF-30 and carboxyl⋅⋅⋅carboxyl dimers in HOF-30a has been unveiled by single-crystal and powder X-ray diffraction. In addition, HOF-30a enables the selective adsorption of propyne over propylene according to single-component sorption and breakthrough experiments. The preferred propyne location in HOF has also been identified by SCXRD test.